AGC Book 20% Cyan Karl Fischer Titration

GTP Brochure

Good Titration Practice™ in Karl Fischer Titration

EDITORIAL

Dear Reader METTLER TOLEDO has an excellent knowledge in any kind of moisture and water content determination from % to ppm. It is of crucial importance to select the right analytical method in order to obtain reliable results that ensure quality and properties of the products in a multitude of industries. Karl Fischer titration is the method of choice for water content determination. With the new generation of METTLER TOLEDO compact volumetric and coulometric Karl Fischer Titrators V20/V30, C20/C30 and Excellence combined general and volumetric KF titrators T70 and T90, water determination has reached an unrivaled level of simplicity and security. This helps you to perform your daily tasks in the most optimal way. In this brochure a specific focus is put on how to perform the Karl Fischer titration analysis the correct way. We would like to introduce this to you as part of ‘Good Titration PracticeTM (GTP) in Karl Fischer titration. This brochure comprises detailed background information and recommendations about: • • • • • Chemistry and control of the Karl Fischer titration Practical tips and hints on sample preparation and instrument operation Measures to optimize accuracy and precision of the water determination Selection of the optimal method for water determination of your specific sample Trouble shooting recommendations if results do not coincide with the expectations

This GTP brochure in combination with the application brochure 39 should serve you as powerful tools for trouble-free water determination throughout the whole lifetime of your METTLER TOLEDO KF titrator. We wish you great success and enjoyment

Hans-Joachim Muhr Market Support Manager BA Titration

Rolf Rohner Marketing Manager BA Titration

.............1 The Control Band ..........12 3 Titration control and end point determination..................................32 4..............2 Two-component KF reagent ........2 Concentration determination with di-sodium tartrate dihydrate.......................................9 2............1......8 2...2..........................1............................................3 Consequences for practical applications........................................................................................................................................................................................................2......................................11 2....3 Pyridine-containing reagents .........27 4...16 3.................4 Control parameters in the volumetric KF titration ...........................................................2.........................................................................................................2 Working with the coulometric KF instruments ..26 4...................1 How often should the concentration be determined?.................................................18 3............2 Coulometric KF analysis..........................1 Filling the coulometric cell .............................................................3 The Cautious start ......4 1..36 4....................2 The drift ...................4 Polarization current and end point........28 4..................................................6 Termination parameters for both coulometric and volumetric KF titration......1 Volumetric KF reagents.................7 2.....5 The solvent.5 Control paramaters in the coulometric KF Analysis ...........3 Secure draining and filling of the titration cell: SOLVENT MANAGER..............4..................................................................................1..............................................2 End point and polarization current............33 4..........................4 1...............4..3.....................................3 Iodine generation.26 4........................................................................................21 3.................................................................20 3.....1........3 Stirring speed and dispersion of the volumetric KF titrant.....3.......................................28 4....1 Indication ................8 2..............................................................................................................................................5 1......0 mg/g .........................................19 3.3 Concentration determination with Water Standard 10............................................................37 4.2........................................................................................7 2........14 3.................................................1 An historic overview ...................1 Principle of bipotentiometric indication ...................................................................................2......................22 3...........3.....................................................4............4..........13 3................................4......................................................................................................3..........................................................6 General recommendations ................................................10 2..........3.....................................................................................2.1.....5 Karl Fischer reagents with ethanol ...............................................................................................35 4...............11 2........1..................................4...................................................13 3........................... The Karl Fischer titration.............................................................29 4.................................8 2...4 Generator electrode without diaphragm ...........3 Volumetric KF Titration: Titrant concentration.................................2....18 3............1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration .................3.......33 4...2 The Karl Fischer chemical reaction ...............................................................................16 3...........19 3.............2 Reaction rate ...............34 4...............................................6 2 Volumetric and Coulometric Karl Fischer Analyses .........9 2................5 Cleaning the measuring electrode ..............................................................4 Cleaning the coulometric KF titration cell.....1 KF coulometry ........26 4......21 3..........4 Special reagents for aldehydes and ketones.1 One-component KF reagent ...........METTLER TOLEDO Good Titration PracticeTM in KF Titration Contents 1 Fundamentals of the Karl Fischer titration .............1 Titration stand ..2.............................................2.........................2 Stoichiometry of the coulometric KF rection ..........9 2..............6 Dissolving capacity of the solvent ................................2 The minimum and maximum dosing rate ......................................................................1.39 1 ............4 Concentration determination with pure water.............................................1...............................33 4.......................................2............5 Application tips ..6.7 2..................................29 4................................1 The influence of atmospheric humidity (drift determination) ......................5 Limitations for the use of the cell without diaphragm......................38 5 Sampling ....................................................................................................................................19 3...24 4..13 3..1.......................2 When do you have to replace the electrolyte? ..........................

.........................................87 11.................................................6.....................................inorganic ....................3 Titration Methods .............................2 Storing the sample ..........1..........................................................58 7................................2 Side reactions ......................58 7...1 Liquid samples ........1 Solids: Characteristics.......................................................................................................79 11......................................................3 Reaction with iodine .................................2 Inorganic chemicals ......68 9 Interferences .......1 Resolution and detection limit ................................6 References.................1 Volumetric methods ....71 9..2 Foods and technical products ..............................................................57 7............77 11...............................................3 Technical products – organic ......................4 Example: reevaluation of side reactions ....3 Amount of sample .............................4 Liquids: Sample input.............................................................................................................................77 11....................86 11......................................3 Procedure...........................................................................62 8 Measurement results ............................................39 5...............................................................METTLER TOLEDO Good Titration PracticeTM in KF Titration 5............................................................................................3......70 9.................60 7......................................................................................................................................................................79 11............................................................................................1 Coulometry.................................................................................86 11.............................5 Accessories for sample input ......................................2 Reaction with water........................................2 Volumetric Karl Fischer Titration ..............54 7...................71 9...................................................................1 Organic and inorganic chemicals ......73 10..................1 Internal extraction .3 External dissolution ........................................6....................................1 Taking the sample................5 Determination of water in gases ..............................................................................................1...............................................39 5.............................................................................................................................2 Liquid samples ....75 11 Karl Fischer Titration: The Method at a Glance ..............................81 11..........................................................................................1...............6 Determination using the drying oven .....................................40 6 Sample addition ............................................................................................................................................................................................1 Reaction with methanol...............................6......................1.......77 11..........................................................1 Solid samples.83 11.................................................................5 Additional literature .....................................................78 11....2...........................................................................87 11..............................89 12 Appendix ..................................71 9..................................................................................................................................1 Effects of temperature....3..............................1...............................48 7....................................70 9...............................................................67 8...................................79 11.............................................................................................................................................................6..........................................................2 External extraction .2 Measurement accuracy.......................55 7..................................4........................................67 8..............................................................................................................................................................80 11.......................47 7.....................................3 Repeatability .....3 Liquids: Characteristics ...............5 STROMBOLI automatic oven sample changer ........................................................................................................................78 11................................2 Coulometric methods ..................................................................................2.....................................................................................................................................................................................................4........................................67 8.....................................2 Solid samples..................................................................83 11...............................4 Technical products ............................................................4.....................................4 Manual Karl Fischer drying oven........49 7..............................90 2 ...........87 11..............................................................................6.................................................................2...............85 11........2...............................................5 Technical natural products ...............................43 6......................................4..........4 Lyophilized substance in septum bottles................................................................58 7....80 11...................2 Purge gas..........4......................70 9...............................72 10 Troubleshooting ...................................43 6.4.59 7........45 7 Release of water from the sample ............................................................................73 10.............................................................................................................4 Sample preparation and input ..................1 Organic Chemicals...88 11...1 Principle ...........................2 Solids: Sample input ......................1...............86 11...................................6 Food ....................

.....4....98 13..............95 12............................98 3 .........4................................5 For acids and bases (pH value) .......5 For acids and bases (pH value) ....................91 12.........................6.....1 Formula for the external extraction ....4 For ketones and aldehydes.............3 Standards for Karl Fischer coulometry..................................93 12.........................96 12...........4...........................................................................................95 12......................1 For samples that are soluble in methanol or ethanol ................95 12.........................................................................2 Formula for the external dissolution ....90 12.........................2 For samples that are poorely soluble in methanol or ethanol ...........91 12................................................6..............................4 Reagents and solvents for coulometric analysis ...............................METTLER TOLEDO Good Titration PracticeTM in KF Titration 12.........98 13.95 12......................................................................................2 For samples poorly soluble in methanol or ethanol........................................2 Two-component reagent: ...........................................................................6 Titrants and solvents for volumetric analysis .....................................4 Safety data for the KF-components and auxiliary solvents: ...6..................94 12...................6...............4.......................1 For samples soluble in methanol or ethanol .......3 For samples that are insoluble in methanol or ethanol ...........................................................98 13................................................................1 One-component reagent ........................92 12...........................4.................................................98 13........4 For ketones and aldehydes......................5 Water Standards for Karl Fischer volumetric titration...............................................................................93 12..........3 Reagents for coulometry: .......................................96 12...97 13 Hazards and waste disposal tips ..............................................................................3 For samples insoluble in methanol or ethanol........6....92 12........92 12..........

First microprocessor controlled KF titrator (METTLER DL18) with automatic drift compensation. Water standards (10.1 mg/g) with test certificate according to DIN 50049-2.0.0. and DL67/70ES/77 Titrators Introduction of the METTLER TOLEDO DL31/DL38 KF Titrators with dedicated fuzzy logic control.J. Meyer and C. Eberius [3]. Enormous spread of the use of KF titration. DO185 Drying Oven for the DL18 Karl Fischer Volumetric Titrator. S. April 1956.Direct method”). Peters and J. by G. Introduction of the METTLER TOLEDO Titration Compact Line V20/V30 and C20/C30 Karl Fischer Instruments.3 First titrator (METTLER TOLEDO DL55) with online curves E = f(t) and V = f(t) for Karl Fischer titration. Pyridine-containing two-component reagents and dead-stop titration instruments are commercially available.5% and 1%. Publication on stabilized single-component Karl Fischer reagent by E. Pyridine-free KF reagents are commercially available. First coulometric KF titration instruments are commercially available. Automatic KF titration instruments with piston motorized burettes. They replaced the DL18/35 KF Volumetric Titrators. Introduction of the METTLER TOLEDO DL32/39 KF Coulometers (generating cell with and without diaphragm). Introduction of less poisonous KF reagents based on ethanolic solution. DL37 KF Coulometer from METTLER TOLEDO. 1.1 1935 1943 1950 1952 1955 1956 An historic overview Publication: "Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern" by Karl Fischer [1]. “Testing of mineral oil hydrocarbons and solvents: Determination of water content according to Karl Fischer . and solvent dispensing and removal. METTLER TOLEDO RONDO Sample Changer with Karl Fischer Kit for automated KF volumetric determination. First diaphragm-less cell for coulometric KF titration. Wernimont and F. promoted by publications by E. First German DIN standard for the Karl Fischer titration (DIN 51777. First fully automatic KF titration with laboratory robots (METTLER DL18 and ZYMARK). 2000 2001 2002 2008 4 . Hopkinson [2]. Solid KF Oven Standards with water contents of 5. Introduction of the METTLER TOLEDO STROMBOLI KF Oven Sample Changer. Publication: Coulometric Karl Fischer Titration by A. M. Use of Karl Fischer method spreads. D. respectively. titrant specific standard parameters and LEARN titration. Jungnickel. 0.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1 Fundamentals of the Karl Fischer titration 1. Publication: “The Dead-Stop End Point“. 1959 1960 1970 1980 1984 1985 1989 1990 1995 1997 1998 New DV705 KF Titration Stand with very low drift value (< 2μg/min) for the METTLER TOLEDO DL53/55/58.Boyd [4]. L. Improved METTLER TOLEDO DO307 KF Manual Drying Oven.

In an alcoholic solution. Bunsen [5]: Karl Fischer discovered that this reaction could be used for water determinations in a nonaqueous system containing an excess of sulfur dioxide [1]. This is formed from sulfur dioxide and methanol according to the equation: 2 CH3OH + SO2 → CH3OH2+ + CH3OSO2- The higher the pH of the solution. W. it is necessary to neutralize the acids that are formed during the process (HI and H2SO4). it only acts as a buffering agent and can therefore be replaced by other bases. The rate of the Karl Fischer reaction. In an alcohol-free solution. the more methyl sulfite is formed by the capture of protons. Methanol proved to be suitable as a solvent.5. C.. Verhoff and E. In the pH range 5. Py•SO3 + H2O → 2 Py-H+I– + Py•SO3 – Py-H+HSO4 – Further studies conducted by J. the reaction between iodine and water takes place in the stoichiometric ratio of 1:1. At pH values above 8. depends on the pH value of the medium (see graphics below) -d[I2]/dt = k • [I2] • [SO2] • [H2O] One possible explanation for the influence of pH on the reaction rate is that it is not the sulfur dioxide itself that is oxidized by iodine under the influence of water. In order to achieve an equilibrium shift to the right. Smith. all the sulfur dioxide is present as methyl sulfite. i. the reaction between iodine and water takes place in the stoichiometric ratio of 1:2: 1. I2 + SO2 + 3 Py + H2O → 2.e.2 The Karl Fischer chemical reaction I2 + SO2 + 2 H2O → 2 HI + H2SO4 The water content determination is based on the reaction described by R. Karl Fischer used pyridine for this purpose. methanol not only acts as a solvent but also participates directly in the reaction itself. and the faster the rate of the Karl Fischer reaction. Py•SO3 + CH3OH → 2 Py-H+I– + Py•SO3 – Py-H+CH3SO4 According to these equations.5 to 8. described by the rate constant k.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1. the 5 . Bryanz and Mitchell [6] formulated a two-step reaction: 1. Barenrecht [7] on the subject of the Karl Fischer reaction have revealed that: • • Pyridine is not directly involved in the reaction. but rather the methyl sulfite ion. I2 + SO2 + 3 Py + H2O → 2. the maximum reaction rate is reached here and cannot increase further.

→ → (RNH) · SO3 R (RNH) · SO4 R + 2 (RNH)I 1. diethylene glycol monoethylether) [10. Methanol should therefore always be present in the minimum required amount. Scholz developed a pyridine-free Karl Fischer reagent with imidazole as base [8]. A.g. Barendrecht [7] observed an increase in the titer with water contents greater than 1 mol/L. this results in a more sluggish endpoint and higher iodine consumption. On the basis of this knowledge. but also facilitated faster and more accurate titrations because imidazole buffers in a more favorable pH range than pyridine. • Influence of the water content of the sample on the Karl Fischer reaction The water content of the sample also influences the H2O:I2 molar ratio. methoxyethanol. dimethylformamide) Studies by Eberius [3] showed that iodine and water react in the ratio of 1:1 if the percentage of methanol in the solvent is 20% or more. in a titration. you should adjust the pH value to the ideal range by adding buffering agents (for acids: imidazole. and for bases: salicylic acid). ROH + SO2 + RN 2.g. This improves the titer stability.3 • Consequences for practical applications Influence of pH on the Karl Fischer reaction Since the maximum rate of the Karl Fischer titration is in the pH range 5.5 to 8.METTLER TOLEDO Good Titration PracticeTM in KF Titration reaction rate increases due to side reactions between iodine and hydroxide or methylate ions.g. is not a serious limitation because the water concentration in the solvent is usually much less.g. J. This reagent not only replaced the toxic. 6 . for determination in ketones or aldehydes). and references therein]. ethylene glycol monomethyl ether. Experiments on the stoichiometry of the reaction showed that methanol can in fact be replaced by other alcohols (e. Verhoff and E. (RNH) · SO3 R + 2 RN + I2 + H2O This resulted in the general chemical equation: ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I E. you can use other alkohols such as. ethanol. Seubert [9] identified methylsulfite in KF solutions with the aid of IR spectroscopy and isolated and identified methyl sulfate as the secondary product of the KF reaction. pH values less than 4 and greater than 8 should be avoided in practice. Scholz resulted in the following reaction scheme being proposed for the Karl Fischer reaction [8]: 1. Scholz was also able to confirm the existence of basic methylsulfite in methanol/SO2/I2 solutions during the titration.C. however. With acidic or basic samples. for instance. In 1988. • Influence of the solvent on the Karl Fischer reaction The stoichiometry (molar ratio of H2O:I2) depends on the type of solvent: Alcoholic solvent Non-alcoholic solvent H2O:I2 = 1:1 H2O:I2 = 2:1 (e. methanol) (e. 2-propanol. Studies by E. E. If a methanol-free titrant has to be used (e. pungent pyridine. This.

1 mg/mL for samples with a water content of less than 200 ppm.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2 Volumetric and Coulometric Karl Fischer Analyses The determination of the water content according to Karl Fischer is nowadays performed by two different techniques: – – Volumetric Karl Fischer Titration.1. where iodine is generated by electrochemical oxidation in the cell The selection of the appropriate technique is based on the estimated water content in the sample: Volumetric Karl Fischer Titration Iodine is added by a burette during titration.e. The drop in titer. You can also use a methanolic solvent mixture specially adapted to the sample as the solvent. The reagent can be stored for approximately two years. Suitable for samples where water is present in trace amounts: 1 ppm .5% 2.100% Coulometric Karl Fischer Analysis Iodine is generated electrochemically during titration. where a solution containing iodine is added using a motorized piston burette.1 Volumetric KF reagents 2. The solvent is methanol. dissolved in a suitable alcohol. The reagent is available in three different concentrations: 5 mg/mL for samples with a water content of 1000 ppm to 100%. sulfur dioxide and imidazole. the decrease in concentration. Suitable for samples where water is present as a major component: 100 ppm . is approximately 0. 7 . 2 mg/mL for samples with a water content of less than 1000 ppm.5 mg/mL per year in a sealed bottle..1 One-component KF reagent The titrant contains iodine. Coulometric Karl Fischer Analysis. i.

imidazole. HYDRANAL® (Composite 5K and Working Medium K. increases their lifetime.g. or an alcoholic mixture. Reagents One-component Two-component 2. stable titer. provided that the bottle is tightly sealed. titration speed slower. such as amines. from VWR/MERCK) are commercially available to prevent this problem. The solvent contains sulfur dioxide. dissolved in methanol. – Titer less stable. Note that it may be necessary to adapt the end point value in the titration method to these reagents.g. One-component reagent: The titrant contains iodine. methanol). leading to higher water contents and a vanishing end point. reagents containing pyridine are still used because they are cheaper and can be made in-house. e. As a result. To improve stability. whereas the solvent consists of sulfur dioxide and a base. + Simple handling. some manufacturers also sell the titrant separated into solution A (sulfur dioxide. It is available in two different concentrations: • • 5 mg/mL for samples with a water content of 1000 ppm to 100%.2 Two-component KF reagent The titrant contains iodine and methanol. The titrant has a stable titer. Both the components are very stable in storage. A titration speed two or three times as high can be achieved with the two-component reagent. sulfur dioxide and pyridine. This special reagent is also suitable for substances that react with methanol. These solutions are mixed 1:1 just before use to form the one-component titrant.1. Some manufacturers have slightly increased the pyridine content in the titrant to achieve a higher titration speed. imidazole and methanol. High titration speed.3 Pyridine-containing reagents Despite the existence of pyridine-free reagents. whereas the solvent contains 2-chloroethanol and trichloromethane.g.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2. dissolved in an alcohol (usually methanol).1. favorably priced. The titration takes slightly longer than with the standard KF reagent. Solvent capacity restricted. sulfur dioxide and 2-methoxyethanol. pyridine. imidazole.1. methanol) and B (iodine. methanol. and results in higher titration speed. apura® (CombiTitrant 5 Keto with CombiSolvent Keto. 2. The solvent is either methanol or consists of methanol mixtures. from Sigma-Aldrich) and e. One-component reagent: The titrant contains iodine.g. 2 mg/mL for samples with a water content of less than 1000 ppm. The separation into titrant and solvent improves stability of the KF reagents. which allow for fast and accurate Karl Fischer titrations.4 Special reagents for aldehydes and ketones Aldehydes (R-CHO) and ketones (R-CO-R) form acetals and ketals if titrated with standard methanol-containing reagents. e. 8 . additional water is produced and titrated at the same time. Special methanol-free KF one-component reagents such as e. Two-component reagent: The titrant contains iodine dissolved in an alcohol. This reagent is declared as “rapid”.

9 . diethanolamine and ethanol. however. The titrant contains iodine and ethanol. These reagents also allow for titration of several ketones which form ketals considerably more slowly in ethanol than in methanol. The classical coulometric cell consists of two parts. ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I In coulometry.→ I2 + 2 e Iodine generation occurs at a generator electrode* (also called “generator cell”. The generator is close to the measuring electrode*. or “inner burette”) incorporated into the glass titration cell.5 Karl Fischer reagents with ethanol Since ethanol is less toxic than methanol. whereas the solvent contains sulfur dioxide. a double pin platinum electrode. Both parts are separated by a diaphragm. 2. the anode compartment and the cathode compartment.1 KF coulometry Coulometric KF determination of water is based on the standard reaction equation for the KF reaction. imidazole.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2. the iodine is generated electrochemically by anodic oxidation in the coulometric cell according to the following half-reaction: 2 I .2.2 Coulometric KF analysis 2. * The terms "generator electrode" and "measuring electrode" mean an arrangement of two electrodes (anode and cathode) to form an electrolytic cell. ethanol-based reagents were launched in 1998. two-component.1. which is monitoring the potential of the sample solution by voltametric technique during coulometric titration.

The negative iodide ions release electrons at the anode and form iodine.g. I2. Note that methyl sulfonic acid. i. used to generate iodine.→ H2 + 2 RN Ammonium ions are then reduced with the formation of hydrogen and a free amine. I-. the catholyte should be replaced once in two weeks. This consists of sulfur dioxide. octanol. is the quantity of charge that is transported by a current of 1 ampere in one second. the KF electrolyte which is required for the oxidation in order to generate iodine by applying a current at the generating electrode. C. which subsequently reacts with water. C. 1C=1A·1s On the other hand. To calculate it. iodine reacts with water.METTLER TOLEDO Good Titration PracticeTM in KF Titration The anode compartment contains the anolyte. other solvents such e. The cathode compartment contains the catholyte. This can cause the cathode to become black.2 Stoichiometry of the coulometric KF rection The amount of water titrated by coulometric technique is determined by the amount of electrical current given in Coulomb. i. hexanol or ethylene glycol may be added. An ammonium salt is added to the catholyte in order to promote hydrogen production. CH3SO3H. Subsequently. The value 96845 C/mol is known as the Faraday constant. 2 I. 2. present in the anolyte compartment. Methanol or ethanol is used as solvent.2. it is necessary to first recall the definition of 1 Coulomb: one coulomb. are oxidized to one molecule of iodine. The catholyte is either a manufacturer-specific special reagent.→ I2 → H2O 10 . or the same reagent as used in the anode compartment. To avoid this.e. as chloroform. the positive hydrogen ions are reduced to hydrogen. 96485 C of current are needed.e. In Karl Fischer reaction two iodide ions. Cathode reaction At the cathode. 2 [RN]H+ + 2e. iodine is generated from iodide by electrochemical oxidation. can reach the cathode where it is reduced to a sulfide compound (obnoxious smell!). Depending on the application. This is the main product formed. Anode reaction At the anode. the reagent that enables completion of the whole electrochemical reaction: the oxidation reaction in the anolyte compartment is completed by a reduction reaction in the catholyte compartment. imidazole and iodide salts. it is known that to produce one mole of a chemical substance that requires one electron. releasing two electrons at the anode.

4 Generator electrode without diaphragm with diaphragm without diaphragm The first commercially available diaphragmless cell for KF coulometry was introduced in 1989. With standard conductivity values.e. This gives an iodine generation rate which corresponds to a maximum of 2240 μg water/min. For an electrochemically optimized Karl Fischer cell. it is used as a reference method for the determination of water content.METTLER TOLEDO Good Titration PracticeTM in KF Titration Therefore. this calculation can be expressed as follows: 1 mg of water corresponds to a consumption of 10. Since the molar mass of water is 18. Since current and time can be accurately measured.). the coulometer operates with current pulses of 400 mA. For this reason. Nevertheless. 200 and 100 mA.3 Iodine generation Iodine is generated by means of current pulses of 400. the maximum possible current applied by the instrument is 100 mA. 300. it is strongly recommended that the coulometer is regularly checked by measuring a certified water standard. hexanol. The rate of iodine generation is adjusted by varying the pulse duration and frequency and the pulse height (in mA).2.712 C electrical current. etc. At very low conductivities (i. no standardization of the coulometric KF reagents is necessary. The main advantages compared to cells with diaphragms are: no contamination or blockage of the diaphragm easier cleaning lower drift 11 .2. As a consequence. 2 x 96485 C/mol is required for 1 mole of water. In addition. the conductivity of the anolyte is influenced by the samples and additional solvents (chloroform. 2.015 g/mol. The maximum pulse height depends on the following factors: conductivity of the anolyte voltage at the generator electrode surface of the generator electrode The voltage at the generator electrode and the surface of the electrode depend on the type of coulometer. the current conversion efficiency for iodine production is assumed to be 100%. 2. coulometry is designated as absolute method. less than 3–4 μS/cm).

This effect is further enhanced by the small dimensions of the cathode. The purpose is to prevent that iodine molecules generated at the anode are immediately reduced to iodide ions at the cathode instead of reacting with water. the cathode is a small-size pin). The diaphragmless cell is ideal for the determination of the water content of the following compounds: hydrocarbons . Thus. Note that hydrogen gas generated at the cathode is forming gas bubbles around its surface.ethers ketones (with special reagent) .acetamides etheric oils and essences . it is still possible for a very small amount of iodine to reach the cathode.. etc. The latter can thus react more efficiently with water. for measurement of samples having a very low water content (e.chlorinated hydrocarbons alcohols . R-NO2 + 3 H2 → R-NH2 + 2 H2O Besides this. and for very accurate determinations. a relatively high stirrer speed allows for more rapid distribution of the generated iodine molecules. In addition. the relative error due to this effect can be minimized by using a larger amount of sample.e. especially when easily reducible.g. Nevertheless.phenols (most) esters . 12 .2.METTLER TOLEDO Good Titration PracticeTM in KF Titration Originally. especially for nitro compounds such as nitrobenzene. other easily reducible substances such as unsaturated fatty acids. In practice. the cell with diaphragm may yield more precise results. lower than 50 μg water/sample). To avoid this concurring reaction. this makes it almost impossible for iodine to reach the cathode and be reduced to iodide. may also be reduced at the cathode by the formation of water. The cathode is smaller and made in such a way that iodine cannot reach the cathode (i. This is a very good reducing agent.edible oils petroleum oils A cell with diaphragm is required for: samples with a very low water content (< 50 μg water/sample) very accurate determinations nitro compounds unsaturated hydrocarbons. However. a different geometry is used for the generating cell without diaphragm. the generator cell was first built with a porous ceramic frit (diaphragm) separating the inner cathode compartment from the anode compartment. Nascent hydrogen is formed at the cathode.5 Limitations for the use of the cell without diaphragm The cell without diaphragm is not suitable for samples that are easily reduced. 2.

1 Indication 3. . The control of the titration is only possible if the end point is indicated.the reaction rate of the Karl Fischer reaction . and hence. Only then can the titrant consumption or the generated iodine amount be determined with the desired accuracy.the stirring speed and mixing of the sample solution.the viscosity of the solution and its temperature. constant AC current – the polarization current "Ipol" – is applied to a double pin platinum electrode.1 Principle of bipotentiometric indication A bipotentiometric indication is used for the volumetric Karl Fischer titration as well as for the coulometric analysis (in electrochemical terminology this is also called "2-electrode potentiometry"). Ideally. the water content. .METTLER TOLEDO Good Titration PracticeTM in KF Titration 3 Titration control and end point determination The addition or generation of iodine must be controlled. The resulting titration speed depends on the following factors: . A small. • • • As soon as all the water has reacted with iodine. • • As long as the added iodine reacts with the water. A high voltage is necessary to maintain the specified polarization current at the electrode. 13 . and the addition or production stopped exactly at the end point.the addition speed or generation rate of iodine . 3. the titration is terminated. there will be free iodine in the titration solution.the termination of the analysis. iodine should be added or generated as quickly as possible. Free iodine causes ionic conduction and the voltage needs to be reduced to keep the polarization current constant. .1.the control algorithm and its parameters. there is no free iodine in the titration/anolyte solution. When the voltage drops below a defined value.

the polarization current. respectively.the solvent or anolyte used in the instrument. the titration end point is reached if the potential at the polarized platinum double pin electrode drops below a specific predefined value. This free iodine gives rise to "ionic conduction". then releases the electron again at the positively charged platinum pin and is again oxidized to iodine. The end point value mainly depends on .(to a lesser extent) the type of electrode (i. Iodide ions. At the end of the titration: As soon as all the water in the sample has reacted with the iodine. Now a low voltage of 50 mV to 100 mV is required to keep the polarization current constant. 3. The iodine is present only at low concentration. If mixing is poor.2 End point and polarization current The Karl Fischer titration is terminated when an excess of iodine is detected in the titration cell. A voltage of ca. This drop in voltage is used to indicate the end of the titration. Ionic conduction Iodine takes up an electron at the negatively charged platinum pin of the indicator electrode and is thereby reduced to iodide (I-). The two negatively charged iodide ions are attracted by the positively charged platinum pin.e.METTLER TOLEDO Good Titration PracticeTM in KF Titration • The ionic conduction takes the following course: an iodine molecule is attracted by the negatively charged platinum pin. again. Above all. Ipol . This leads to a termination of "ionic conduction" and the measurement signal becomes unstable. where they donate the electrons and form an iodine molecule. this value depends on the polarization current. there is no free iodine in the titration/anolyte solution. Thorough mixing of the titration/anolyte solution is necessary in order to achieve constant "ionic conduction". • • At the beginning and during the titration: As long as the iodine generated reacts with the water. geometry and dimensions of the metal parts) . . It then acquires two electrons and turns into iodide ions (2 I–). 14 . free iodine is present in the titration/anolyte solution. I2. which are present in excess in the titration solution. no iodine reaches the negatively charged platinum pin.e. i. 400 mV to 650 mV is necessary to maintain the set polarization current at the double pin electrode.1.

Influence of the sensor The potential jump at the end of the titration is also influenced by the geometry (surface and design) of the platinum sensing material of the sensor.e. this leads to a larger potential jump compared to a cleaned or a new sensor (without layer). a double ring or plates instead of rings. The current density can be compared to a water pipe where a specific water has to flow. In general the larger the platinum surface the smaller the current density. On the other hand. pin length: 3 to 4 mm. and subsequently it remains constant. and increases the risk of over titration.e. on the other hand. a lower polarization current gives a smaller and steeper potential jump at the end of the titration. The condition of the sensor has an influence on the potential jump Platinum is a strongly adsorbing metal. With use. exhibit a smaller potential jump.METTLER TOLEDO Good Titration PracticeTM in KF Titration For the volumetric KF titration. Sensors with a large platinum surface. pin length: 3 . With used sensors. Sensors with short platinum pins (< 3 mm). As a consequence. i. Which polarization current should be used? A higher polarization current requires a larger iodine excess (indicated by a pronounced yellow coloration of the titration cell solution) to achieve ionic conduction for the determination of the end point. a layer is formed on the surface of the platinum pin sensor. with longer pins. the following values have been obtained with a C20/C30 KF Coulometer (double pin platinum sensor. its surface can easily bond suitable chemical compounds. The larger the diameter of the pipe. i.4 mm. and increases the sensor resistance. the polarization current should be set as low as possible. pin diameter: 1 mm): AC Polarization current / µA 5 Endpoint / mV 100 The same end point values can be used for ethanol based KF coulometric reagents. exhibit a larger potential jump and also a higher end point. pin diameter: 1 mm): AC Polarization current / µA 24 Endpoint / mV 100 For the coulometric KF analysis. the lower the pressure needed to transport the desired amount of water through the pipe (= smaller pressure difference). However. just after the equivalence point. This makes it more difficult to stop the titration at the right moment. The layer is formed during the first ten titrations. iodine excess should be as low as possible to get accurate results.g. e. 15 . the following end points have been defined for methanolic one-component and two-component KF reagents using a V20/V30 volumetric KF titrator or T70/T90 Excellence titrator (double pin platinum electrode.

the water concentration. and the reaction rate also decreases: iodine must be generated or added more slowly because a small water amount is still present. 2. note that sulfur dioxide is added only in slight excess with the iodine titrant solution when using one component titrant. If the speed is too slow. 3. In the volumetric KF titration. It is consumed with each additional measured sample leading to a decreasing dioxide concentration. sulfur dioxide is present in large excess in the anolyte. the water concentration is lower.and on the iodine concentration.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3. a large excess of sulfur dioxide is present in the solvent. Karl Fischer titrations with the two component reagent are thus significantly faster than with the one component reagent.0 mL In the coulometric KF analysis.2 Reaction rate The reaction rate of the Karl Fischer titration depends on: . with the twocomponent reagents. 3. Towards the end of the titration. At the beginning. stirring speed. Stirring speed The optimum stirring speed is obtained when a distinct vortex is visible. Mixing is influenced by the 1. If 16 . and overtitration may occur. which gives a high reaction rate.2 min with a titrant consumption of 2. irregular. the titration may also be too slow.d[I2] / dt = k · [I2] · [SO2] · [H2O] In addition.the sulfur dioxide concentration. Example (V20/V30/T70/T90): One-component reagent Two-component reagent 2-3 min with a titrant consumption of 2. On the other hand. [H2O] . As a consequence. This results in a reaction rate up to 2 times faster for the two component reagent than for the one component reagent.5 .0 mL 1. the water content is high. shape of the vessel (volumetric KF titration). point of titrant addition (volumetric KF titration). [I2] . the pH value of the solution has a strong influence on the rate and in particular on the stoichiometry of the Karl Fischer reaction. [SO2] . Iodine generation or addition is usually the rate determining factor. lower reaction rates are achieved with anolyte solutions that have been used for a long time.3 Stirring speed and dispersion of the volumetric KF titrant Good mixing is essential for fast and accurate KF titrations. Iodine generation or addition can proceed rapidly because iodine immediately reacts with water.

Bubbles falsify the measured values. turbulence is not achieved and the mixing effectiveness is lower. Point of titrant addition The titrant should be added where the turbulence is the greatest to ensure efficient mixing. 17 .METTLER TOLEDO Good Titration PracticeTM in KF Titration bubbles form into the solution. but rather along the base directly towards the sensor. This is essential for a fast reaction rate and for short titration times. Iodine would not be distributed upwards. Vessel shape The conical shape of the beaker and the short stirring bar lead to turbulence at the point of titrant addition that effectively disperses the titrant. the point of addition should be sufficiently far away from the sensor to allow for sufficient time for reaction. If a longer stirring bar is used. Furthermore. Otherwise the sensor may directly detect added iodine. leading to slower addition and longer titration time. the stirring speed is too fast.

1 The Control Band The control band is a modifiable control parameter for both types of KF reagents. The following drawing reveals a schematical illustration of the control band: 18 . Cautious The volumetric KF methods of the V20/V30 as well as T70 and T90 use KF titrant specific titration control parameters. An overview of the control parameters is given as follows: Volumetric KF Titration End point Control band Dosing rate (max) Dosing rate (min) Start: Normal.4. The dynamic behaviour of the control can be influenced by a variation of the control band.4 Control parameters in the volumetric KF titration Several parameters can be defined in the titration method in order to optimize the method for the samples and the reagents. The recommended standard values are listed in the following table: Recommended standard values Sensor Ipol [µA] Stirrer speed [%] End point [mV] Control band [mV] Dosing rate (min) [µL/min] Dosing rate (max) [mL/min] Start Driftstop relative [µg/min] 1-Comp titrant 24 35 100 400 80 5 normal 15 2-Comp titrant 24 35 100 400 100 3 normal 15 3.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3.

e. 19 . The closer the potential to the end point. the titration will take too long.3 The Cautious start If the water content is very low. You should select Start: Cautious for one and two component reagents if the amount of water in the sample is less than 500 µg.e. In this case you can activate the Start: Cautious parameter.4.The dynamics of the control can be influenced in the following way: Increase of the control band Aggressive control Smooth control Two different controls are used for 1-Comp and 2-Comp titrants. The following points represent possible contributing factors: contaminated or old sensors. In both cases (normal and cautious mode) the maximum dosing rate will be reached at the end of the ramping up. Dosing rate (max) = 2 mL/min.g.. 2. at higher water contents.4 Polarization current and end point Each end point is valid for a specific polarization current. In particular. With large amounts of water. Recommendations 1. The end point for a specific polarization current is influenced by the sensor and the solvent. the titration starts with a slower acceleration (ramp up) than in the normal mode. the end point must be adjusted. the titrator automatically issues a warning. the control reacts more sensitively to potential changes. 3. Thus. the slower is the titrant addition. if the polarization current changes.4. i.2 The minimum and maximum dosing rate Both rates limit the dosing speed of the titrant to an upper or lower level. longer titration times and poorer repeatability are resulting by selecting a higher end point potential value. The maximum dosing rate is dependent on the actual burette size. 3. In the cautious mode. the titration starts so quickly that overtitration may occur. sensors with very short platinum pins (< 3 mm). if the control band width is decreased. 3. however. Burette size [mL] 1 5 10 20 Maximum dosing rate [mL/min] 3 15 30 60 Remark: Since the maximum dosing rate of a 1 mL burette is lower than the standard parameter 5 mL/min in the case of a 1-Comp titrant. You can also set the maximum dosing rate to a lower value for small amounts of water if you wish the titration to progress more cautiously. which leads to a stronger reduction of the dosing speed. The 2-Comp titrant control reacts more sensitively to a potential drop than the 1-Comp titrant control.4. This is more suited for small water amounts.METTLER TOLEDO Good Titration PracticeTM in KF Titration The titrant addition is calculated on one hand by using the distance of the actual potential from the end point and on the other by using dE/dt.

the system reacts slowly in the case of ethanol based reagents. Therefore it is recommended to decrease the polarization current to about 15 μA. setting up of the titrant as 1-comp KF titrant yields shorter titration times. If one-component reagents are used. The consequences of choosing a too low end point value are illustrated in the figures above: On the right side. table) work fine.g. Therefore the potential jump at the end of the titration is smaller compared to conventional reagents. the titration can be accelarated by reduction of the control band to 300 mV. this results in an illdefined titration end point. the sensor current shall be reduced to 15 μA.5 Application tips Methanol based reagents • The standard parameters listed in the table above are ideal for the titration with methanol-based reagents. the overall ionic conductivity is increased. Auxiliary reagents • If formamide is added to the solvent. Ethanol-based reagents • Compared to the methanol-based reagents. the maximum dosing rate can be set higher for certain reagents: 4 mL/min for Riedel de Haen 2-Comp 5. • If 1-comp titrants are used.METTLER TOLEDO Good Titration PracticeTM in KF Titration - long alkyl chain alcohols. This measure allows the system to cope with the reduced conductivity. If 2-comp ethanolic reagents are used. instead of methanol or ethanol. the overall ionic conductivity is decreased. the control band shall be decreased to 100 mV and the maximum dosing rate decreased to about 50%. used as solvent. up to 8 mL/min for most 2-Comp 2 titrants. • If 2-comp titrants are used. 2-propanol.g. • If Chloroform or Xylene is added in order to dissolve oil samples. the titration curve is more or less flat towards the end. 20 . Composolver E) the standard 1-Comp parameters (cf. In order to achieve a good repeatability. • • If 1-Comp titrants are used with Ethanol (e. This results in a lower voltage required to maintain the polarization current. 3. e.4. which will lead to long titration times and to low precision.

The most straight forward influence on the control behaviour is achieved by a variation of the maximum dosing rate. There is no need to accurately adjust the control band to the actual start potential. 3. In most cases 300 – 400 mV are well-suited. The minimum dosing rate shall be used to fine tune the final phase of the titration. Cautious Generator current: Automatic. Fix (400. However the control band shall not exceed the start potential. 3. If the titration takes too long.6 General recommendations 1. E E t Oscillating system behaviour. In the case of 2-comp reagents over titration can be prevented by reduction of the maximum dosing rate. where the methanol has been replaced by e. which is the case in some ethanolic reagents. In general. the 1-Comp control is suitable for systems that show an oscillating potential behaviour.4. This control is also recommended for 2Comp systems that show a noisy signal at the beginning of the titration. which is the case in 1-Comp systems. ->Use the 1-Comp control Smooth system behaviour ->Use the 2-Comp control t 3. an increase of the control band is recommended. Furthermore it is recommended to reduce the polarization current to a value of 15 μA. 200. 300.METTLER TOLEDO Good Titration PracticeTM in KF Titration KF reagents for ketones • An end point value of 150 mV for both one-component and two-component reagents is recommended when using special KF reagents for aldehydes and ketones. 2. 100 mA) 21 .5 Control paramaters in the coulometric KF Analysis An overview of the relevant control parameters is given as follows: End point Control band Rate: Normal. 2-methoxyethanol.g.

6 Termination parameters for both coulometric and volumetric KF titration The KF titration can be terminated using various parameters. i. The closer the measured potential value from the predefined end point is. 2. the online determination of the drift during analysis has enabled a so-called "drift stop" to be used as a termination parameter.e. 200 and 100 mA. Initially. the slope of the iodine generation rate is flat at the beginning of the titration.e. Later on. the iodine generation is higher than in the cautious mode. or it can be set to a specific value (“Generator current” . maximum titration time. tightly sealed stand).. relative drift stop. less than 50-100 μg water per sample).25 µL for a 5 mL burette). i. During the course of the titration it increases up to the maximum rate at a generating current of 400 mA. Normal: This iodine generation mode is generally used for all water content determinations. pulse frequency and pulse height (mA) are used as variables by the instruments. This parameter shortens the titration time and leads to repeatable results. In addition. iodine is generated by means of current pulses of 400. the slope of the iodine generation is steeper and the rate is increased based on the measured potential value. then the titration was stopped. minimum titration time 22 . Cautious: Suitable for samples of low water content (e. Since the first developed KF reagents reacted slowly.e. the slower is the generation of iodine. it has been possible to reduce the delay time to 5 to 10 seconds due to the introduction of • • • new. and improved KF titration stands (i. as soon as the was potential value was lower than the set end point during the defined delay time. 300. The coulometer provides two different modes for iodine generation under the control parameter “Rate”: 1. 3. pyridine-free reagents with a faster reaction rate. The fixed setting is used for solutions that exhibit a difficult characteristic with respect to conductivity. In particular.e. the pulse height can be automatically changed by the system if in the titration method the control parameter “Generator current” is set to “Automatic”.METTLER TOLEDO Good Titration PracticeTM in KF Titration The iodine generation rate in the C20/C30 Coulometric Compact Karl Fischer Instruments depends on the distance from the end point.Fix). Variation of pulse length (time). More specifically.g. The iodine generation starts slowly. Five termination parameters can be defined in the titration method: delay time. a delayed switch-off time of 10 to 20 seconds was set at the end point. i. absolute drift stop. During the course of the titration it increases up to the maximum rate at a generating current of 400 mA. high resolution burettes (0.

easy to understand (volumetric).METTLER TOLEDO Good Titration PracticeTM in KF Titration Delay time The titration is terminated when the potential remains below the end point for a defined time (e.m the drift before titration) and the relative drift. 5-15 μg/min (volumetric) • Advantage: independent on the initial drift. Typical delay time: 5 . Typical absolute drift stop value: 3 µg/min (coulometric). Thus. the absolute drift stop value must be greater than the initial drift.e. Disadvantage: The value optimized to the initial drift. 10 µg/min (volumetric) • Advantage: Independent on the titrant concentration. otherwise the termination criterion is never satisfied. After the defined time has elapsed. • Advantage: This parameter ensures a high repeatability of the results.Maximum titration time The titration is terminated after the defined time. 15 s) following the addition or generation of iodine. Typical value for the relative drift stop = 2-5 μg/min (coulometric).g. The smallest increment must be sufficiently large to compensate the drift. Absolute drift stop Termination occurs as soon as the actual drift drops below the predefined absolute drift value. especially if working with the KF sample oven. . has to be t/s • Relative drift stop The titration is terminated as soon as the actual drift drops below the sum of the initial drift (i.15 seconds (Coulometric/Volumetric) • • Advantage: well-known method. 23 . Disadvantage: The minimum rate must be adapted to the initial drift and the titrant concentration. the titration is terminated and the result is printed. titrant concentration (volumetric) and side reactions. otherwise the termination criterion will never be reached.

If the water content is relatively high. and the titrant concentration (volumetric). you can terminate the titration at a higher drift (relative drift stop = 40 to 70 µg/min).METTLER TOLEDO Good Titration PracticeTM in KF Titration . This is particularly critical in connection with the "slower" reagents for ketones and aldehydes. This termination parameter is also well-suited when the internal extraction is needed to determine the water content in insoluble sample: The water contained in insoluble samples is extracted during the titration. Two-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability. Maximum titration time for determinations with the KF drying oven When using the drying oven. Thus. 3. • Advantage: This parameter ensures a high repeatability of the results. this is the simplest and most universal parameter to use. you can ignore these traces. possibly resulting in poorer repeatability and lower water contents. It is recommended to be used for substances that release water slowly. volumetric). A relative drift stop of 20 to 30 µg/min shortens the titration time. The reason for this is either a very slow release of the last traces of water or a slow thermal decomposition of the sample. The value of the relative drift stop influences the repeatability and the titration time: • • Drift stop (low value) → better repeatability poorer repeatability → → long titration time short titration time Drift stop (high value) → In particular. soluble samples You should normally choose the relative drift stop as a termination parameter.6. the following values are recommended for volumetric KF titration: One-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability. The final traces are only extracted very slowly. A relative drift stop of 20 to 40 µg/min shortens the titration time without affecting the repeatability. but involves a risk that the titration will be terminated a bit too early. Use the drift/time curve to determine this value.. This parameter is independent of the the initial drift (coulometric. the drift at the end is often greater than the initial drift. The vaporization of water is also irregular in the final stages. i.e. so 24 .1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration The following termination criteria are most commonly used for water determination by Karl Fischer titration: Relative drift stop for trouble-free.Minimum titration time Titration is not to be terminated before this time in [s] is reached (exception: the maximum volume has been reached).

the maximum titration time has proven to be best termination criterion in practice. the titration is terminated at the latest after the defined maximum time. you should take measures to reduce the drift. It gives you the best accuracy and repeatability of results. Therefore. A combination of the relative drift stop and the maximum titration time has proved effective for such samples. (Set the minimum titration time equal maximum titration time). Relative drift stop/maximum titration time for problematic samples Some samples lead to a high drift value at the end of the titration. The higher drift is therefore influenced to a large extent by the sample. If the drift is greater than 10 µg/min. This is the case with samples that only release the final traces of water very slowly or that produce side reactions.METTLER TOLEDO Good Titration PracticeTM in KF Titration that the repeatability of the titration termination using the drift stop parameter is poor. Note: To obtain accurate and reliable results you should only work with the coulometer when the drift is lower than 10 µg/min. 25 . If the drift stop value is not reached.

After the anolyte (coulometer) or the solvent (volumeter) has been added. since cold air cannot absorb as much moisture. The drift. Do not shake too vigorously to avoid solvent gets on the cover of the vessel. • Protect the titration cell with a desiccant (3 Å molecular sieve and silica gel). The drying capacity of the desiccant is limited and it depends on the humidity and can be exhausted after 2 . Moisture can enter the sample. until it is absolutely free of water. The factors include: • • • • the atmospheric humidity the working medium the pH of the sample the side reactions between the sample and the Karl Fischer reagent 4. The following rules should be observed: • • Close all openings in the titration stand. however.1 The influence of atmospheric humidity (drift determination) Atmospheric humidity represents the most relevant source of error in Karl Fischer titration. the residual moisture dissolves more rapidly into the anolyte (solvent). Silica gel can be regenerated over night at 150 °C. the higher the atmospheric humidity in the laboratory. whereas molecular sieves require temperatures up to 300 °C. This can take 1 .4 weeks (indicated by a colour change of the indicator of the silica gel). the relative humidity increases. The Karl Fischer titrator should never be installed close to a ventilator of the air conditioning system! 4.e. The Karl Fischer titration Various factors must be taken into account with Karl Fischer titration to obtain correct results. Briefly. the greater is its influence on the results of the Karl Fischer titration. 26 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. However. The air within the titration vessel also contains moisture. The desiccant absorbs the moisture and protects the titration cell against the ingress of moisture. i. it is titrated to dryness during pretitration. The total moisture can be titrated more quickly by gently moving the vessel from side to side so that solvent swirls up the side of the vessel to pick up moisture adsorbed on the glass walls. The air-conditioning system should therefore be equipped with a moisture condenser. Condition the titration cell before use.3 hours. the titrant and the titration stand. remains high because the moisture present on the glass walls and the air in the titration cell diffuse only slowly into the anolyte (solvent). In this way. This problem is particularly relevant in tropical climates or in coastal regions. there will be moisture on the glass surface of the titration cell and the inserts.1. The assumption that air-conditioned rooms have a lower atmospheric humidity is often not true: the majority of air-conditioning systems simply cool the air.1 Titration stand The titration stand must be sealed as tightly as possible against atmospheric moisture. where the relative humidity can achieve values of more than 80%. When you assemble the titration stand for the first time.

this water amount is also titrated during analysis. This is achieved by titration of the dry solvent for a defined time (drift determination). the last measured drift value is automatically stored. On the other hand. if it is defined as the parameter “Source for drift: Online” in method function “Titration stand (KF stand)”.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. the KF titrator continuously titrates the water that diffuses into the cell. Therefore it must be taken into account when calculating the water content. In the standby titration. and is given in μg water/minute. or it can be entered by the user (“Request”): Source for Drift Online Determination Fix value Request Explanation Last measured value of standby The drift is determined and stored as raw result DRIFT A fixed value is defined into method The value can be entered immediately after starting sample titration The drift value is subsequently used in the calculation of the result in order to compensate for the moisture that entered the titration cell according to the following formula: Sample result = Total amount of water determined . In this respect. traces of water will always find a way into the titration cell. the drift indicates the quantity of water that enters the titration stand over a defined period. the drift value should therefore be as low as possible and stable before the start of a titration! 27 . it is necessary to quantify the amount of water entering the titration cell during titration. and its value is displayed on the screen. At the start of a sample titration. t. Therefore. For accurate results.2 The drift No titration stand is completely water tight. On the other hand. it is also possible to use the value of a previously performed drift determination (“Determination”).1.(drift * titration time). or a fixed value can be defined into the titration method (“Fix value”).

However. when the drying oven is used.Then fill the anode compartment with approx. . the levels slowly become the same. • Titration cell with diaphragmless generator electrode .Make sure that the level of the anolyte is approx.2 Working with the coulometric KF instruments 4.First transfer 5 mL catholyte to the cathode compartment. Note: In production. 100 mL electrolyte solution (anolyte) into the titration cell. .The difference in level between the anolyte and catholyte is maintained as long as the stirrer is in operation. By ensuring that the level of the anolyte is higher than the one of the catholyte. 5 mL from the bottle with a syringe and inject it into the generator electrode or empty an ampoule of catholyte into the generator electrode.1 Filling the coulometric cell • Cell with generator electrode with diaphragm . The catholyte can be dehydrated with a few drops of a volumetric KF one component titrant. Normally this brown coloration disappears on filling the titration cell because the iodine excess is consumed. Higher anolyte level → low drift Lower anolyte level → drift is high .METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. In this case.5 mm higher than that of the catholyte. the level of the anolyte increases. the moisture enters the diaphragm and is slowly released into the anode compartment.Take approx. the level of the anolyte drops due to evaporation. you must add some methanol or sample so that the color changes to yellow. 2. .Pour approx. some anolyte solutions contain an excess of iodide and the solution has a brown colour. 3 .The generator electrode should dip approx. which leads to a higher drift. If this is not the case. If the level of the catholyte is the same or higher. . a flow occurs from the cathode compartment to the anode compartment. 28 .2. . 100 mL anolyte. As soon as the stirrer is switched off.When a sample is injected into the anode compartment. The catholyte always contains traces of water. the anolyte should be topped up from time to time with anhydrous methanol. This can be avoided as it follows: 1. 2.5 cm into the electrolyte solution.

Catholyte solutions (5 mL): after 200 mg water. The Solvent Manager is located on top of the waste bottle and includes strong air pump (diaphragm pump) and an electromagnetic valve. The higher the level in the anode compartment.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. This can lead to wrong results. when using a generator electrode with diaphragm. If the conductivity of the anolyte drops to a very low value. . • • • • • 4. the worse the stirring efficiency will be.Anolyte solutions (100 mL): after 1000 mg water. This can happen if large amounts of samples of low conductivity are titrated. The working principle of the Solvent Manager is illustrated in the following schematical illustrations: 29 .2 When do you have to replace the electrolyte? The electrolyte must be replaced in the following situations: • If the capacity of the electrolyte is exceeded. and the risk of over titration increases. A level sensor in the waste bottle prevents from overflow.3 Secure draining and filling of the titration cell: SOLVENT MANAGER The easiest and secure way of draining and filling the coulometric titration cell is performed with the external KF liquid handling device Solvent Manger. the dissolving capacity of the anolyte (coulometric KF) is exhausted and an emulsion is formed. In the cathode compartment sulfides and mercaptans are formed that lead to an obnoxious smell and a higher drift. After being used for two weeks.g. The capacity is monitored by the coulometers (see operating instructions). If an emulsion forms in the anode compartment. If the drift is too high. . e. it is common use to replace both the anolyte and catholyte at the same time If after adding samples. the drift slowly increases.2. the level of the solvent or the anolyte exceeds the 150 mL mark. It is fully controlled by the titrator. If an electrolyte is used for a long period without replacement. In practice.2. below 10 μS. Any contact with the reagent is avoided during draining and refilling of the titration cell. With poorly soluble samples.

Step 1b: Start the reagent replacement either from the manual function ‘Replace reagent’ or from a predefined Shortcut on the Home screen of the Touchscreen.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 1a: Put the draining and reagent refill tube into the coulometric titration cell. 30 . Step 2: The Anolyte is drained into the waste bottle by applying vacuum.

An optional reagent exchange set consisting of tubes. Step 4: After a predefined time or by manual interaction the pressure within the solvent/anolyte bottle is relieved by switching the magnetic valce into the initial position. Depending on the type of the generator cell the following liquid handling actions can be performed: Diaphragmless generator cell: Replacement of the anolyte Generator cell with diaphragm: Replacement of the anolyte and draining of the catholyte 31 . In this configuration only draining of the titration cell is possible. drying tube and tube holder enables both draining and refilling.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 3: The pump direction is switched by activation of the magnetic valve and subsequently fresh solvent is pumped into the titration cell by applying over pressure of dry air. The Solvent Manager is part of the standard delivery of the C20 and C30 Compact coulometric KF titrators.

The generator electrode with diaphragm must be cleaned periodically because contamination accumulates in the diaphragm over a longer period of time. the most effective cleaning agent is chromic acid. Afterwards thoroughly rinse the generator electrode with water. Methanol flows through the diaphragm and rinses out moisture and contaminants. • Thorough cleaning of the generator electrode If the generator electrode and the diaphragm are strongly contaminated. . then with anhydrous methanol and dry it as described above. which leads to a higher drift.This procedure should be repeated at least once. . . The procedure is identical to that described above.METTLER TOLEDO Good Titration PracticeTM in KF Titration Note: The tubes for anolyte exchange are not left in the titration cell during titration. The C30 provides a reagent monitoring routine which is called Reagent Control.Place the empty generator electrode in anhydrous methanol.Methanol flows through the diaphragm into the cathode compartment.4 Cleaning the coulometric KF titration cell The titration cell and both electrodes should be cleaned. Place the empty generator electrode in the chromic acid or fill the generator electrode with chromic acid and let it flow through. • Cleaning the titration vessel Clean the titration vessel with water or a suitable solvent. Moisture and contaminants are rinsed out of the diaphragm. Simple cleaning and drying of the generator electrode Method A: . • 32 . especially if dirty samples are analyzed. If immediate use is required rinsing with anhydrous methanol shall be applied. since it would cause a higher drift value. Method B: .2.Fill the generator electrode with anhydrous methanol.Afterwards dry the generator electrode at a maximum temperature of 50 °C in an oven or with a hot air dryer. The contaminants can originate from samples or are side products that have been formed in the cathode compartment by reduction. It provides the following: Monitoring three reagent parameters Usable life in days Capacity in mg water Number of samples When due. reagents can be replaced directly out of running method Choice of enforcing the user to replace it immediately or ask again later 4. Afterwards dry the vessel at 100 °C in an oven or with a hot air drier. Drying is not necessary if you use it immediately.

In this case. the one-component titrant. This is sufficient in most cases. 4.01 mg/mL per week. This test of the complete system by a titer determination is therefore an essential condition for accurate. while the two-component titrant is rather stable). and let an electrical current of about 400 mA flow across the platinum pins for 60 s by starting the KF titration: 1) Disconnect the S7 connection of the indication electrode. so that there is a sharp drop in concentration.3. a layer is formed on the platinum surface after the first few titrations. The layer should therefore not be removed by cleaning. The volumetric KF titrators enable monitoring of the usable life and life span of the titrant. The titrant may absorb moisture from the atmosphere reducing its concentration (the anhydrous methanol in the titrant is very hygroscopic) . 2) Connect the S7 connection of the generator cell with the indication electrode. a weekly titer determination would be sufficient (the concentration of the one-component titrant changes by 0. the measuring electrode must be cleaned. In the global settings within the setup menu of 33 . place the electrode in 0. 3. 4.5 mol/L sulfuric acid. This also becomes noticeable through a dark coloration of the anolyte at the end point. e. The tightness of the titration stand and the proper functioning of the burette and the end point indication are also checked at the same time as the concentration is determined. This leads to a higher potential jump. Based on the chemical stability of the titrant.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4.5 Cleaning the measuring electrode Generally. However. A reminder can be set to warn the user at the start of every titration that the usable life is about to expire in the predefined time range (days).if the titrant bottle is not tightly sealed. the tightness of the titrant bottle and the desired level of accuracy. it is better to determine the concentration every 2 to 4 hours. A significant change in temperature may occur: The Karl Fischer titrants consist of approximately 90% methanol or ethanol. In countries where the temperature varies considerably during the course of the day and the lab is not air-conditioned. 2. The titrant is not chemically stable. We recommend to determine the titrant concentration daily. Their volume increases considerably with temperature. 3) Stop the method when the cleaning is finished so that the polarization current at the indication electrode is stopped.1 How often should the concentration be determined? How often the concentration is determined depends on the choice of titrant. which prevents a good indication. the indicating electrode does not need cleaning. • Clean the platinum pin with a paper tissue.g. • With heavily contaminated electrodes. samples may be deposited on the surface of the electrode. The Ohmic resistance of the electrode is increased. repeatable results.if the desiccant on the titrant bottle is "used up".3 Volumetric KF Titration: Titrant concentration The titrant concentration can change due to the following reasons: 1. . As already described.2.

you should first grind it to a fine powder before using it or use special Di-sodium tartrate dehydrate for Karl Fischer Titration Procedure . Determine the weight by back weighing and enter it as sample size. Add it into the titration vessel.: . Mix for 3 minutes to achieve complete dissolution before you start the titration.3 to 2.66% of water.2 Concentration determination with di-sodium tartrate dihydrate General Di-sodium tartrate dihydrate.and at the same temperature.04 and 0. 2. Determine the concentration under the same conditions as for sample analysis.08 g/mol). .e. Since it slowly dissolves in methanol. Under normal conditions. is the primary standard for Karl Fischer titration since it is stable and non-hygroscopic.08 g di-sodium tartrate dihydrate with the aid of a weighing boat. Make sure that nothing adheres to the beaker wall or to the electrode.5 mL with a 5 mL burette.METTLER TOLEDO Good Titration PracticeTM in KF Titration the titrator actions can be defined that will be applied if the usable life or life span is actually exceeded. which prevents the execution of further titrations. - 34 . The plastic tubing is not absolutely water vapor-tight. Na2C4H4O6•2H2O (M = 230. thus the titrant concentration slightly but continuously decreases slightly when left to stand for a long time. 26-50 % of burette volume. Either the user is simply warned or the usage of the expired titrant is blocked.Use the optimized METTLER TOLEDO method M301 Weigh between 0. Note: 1. Rinse the burette 2 times into a waste bottle before you determine the concentration. This sample size yields an optimum titrant consumption of 1. it contains 15.using the same titration stand with the same volume of solvent. 4.3.e. i. i.

0. The water standards are supplied in glass ampoules. A cloudy solution will falsify the results (i. You can perform six determinations in 30 mL of Solvent* before you need to change it. Thus. e. You can perform eight determinations in 40 mL of this mixture before you need to change the solvent.METTLER TOLEDO Good Titration PracticeTM in KF Titration Solubility of di-sodium tartrate dihydrate Di-sodium tartrate dihydrate must be completely dissolved (clear solution!) to obtain correct results. 35 .5 g of water standard 10. In Solvent*/chloroform mixture 1:1 or Solvent*/decanol mixture 1:1 In Solvent*/formamide mixture 1:1 In methanol In methanol/chloroform mixture 1:1 or methanol/decanol mixture 1:1 In methanol/formamide mixture 1:1 In solvent for aldehydes and ketones (one-component reagent) In ethanol *Solvent: solvent for the two-component reagent 4. mixing time 2 to 3 minutes. You must perform the determination in pure methanol! Less soluble. mixing time 2 to 3 minutes. You must perform the determination in pure methanol! Highly soluble. This content is confirmed by the test certificate enclosed with every package. The values obtained are approximately 10% too high.0 mg/g General Water standards consist of a mixture of organic solvents containing a specific amount of water. Procedure To achieve an optimum consumption of 2 to 3 mL titrant with a concentration of 5 mg/mL. Highly soluble.e. The values that are obtained are approx. too high titer).0 to 1. "HYDRANAL®-Water Standard 10. Partially soluble. 30% too high. You cannot perform more than one determinations in 40 mL of ethanol (with 0. You cannot perform more than three determinations in 40 mL of methanol (with 0.g. mixing time 5 minutes.0" from Sigma-Aldrich® with 10 mg water in 10 g standard.3. mixing time 1 minute. you should weigh in 1.05 g di-sodium tartrate dihydrate). They are thus protected against the ingress of moisture and can be stored for up to five years. You must either change the solvent after every sample or use pure Solvent* for the determination. always take into account the limited solubility of di-sodium tartrate dihydrate in the most commonly used solvents for Karl Fischer titrations: In Solvent* Highly soluble.045 g di-sodium tartrate). mixing time 1 minute. mixing time 1 minute. Slightly soluble.05 g di-sodium tartrate). You can only perform one determination in 50 mL of 1:1 mixture (with 0. Less soluble.3 Concentration determination with Water Standard 10. Partially soluble.

4 Concentration determination with pure water General When using pure water to determine the concentration. Determine the weight by back weighing. Draw the whole content of the ampoule into the 10 mL syringe.01 mg (e. Thus. Start the titration without any mixing time. Plastic syringes may introduce a small amount of moisture.5 mL at a time as an aliquot.g. – – – 36 . it is strongly recommended determining the concentration either with di-sodium tartrate dihydrate. 4. Glass syringes are better. 5. In an open ampoule the liquid standard is exposed to air moisture. A balance with a resolution of 0.1 mg does not satisfy the requirements for a repeatable titration.0 µL deionized water with a 10 µL syringe. 3. 4. Use a new ampoule for each new concentration determination. a very good deal of practice and precise working is required to obtain repeatable.0 mg/g water standard.01 g as the sample size. the water content is increased and thus this will falsify the results. Start the titration without any mixing time. Procedure – – You should weigh between 10 and 20 µL of deionized water or water according to ISO 3696 to achieve a consumption of 2 to 4 mL titrant with a concentration of 5 mg/mL. Use the METTLER TOLEDO method M300 The water standard is highly soluble in all commonly used solvents for Karl Fischer titration and can therefore be used without restrictions.METTLER TOLEDO Good Titration PracticeTM in KF Titration – – – – – – Notes 1. Open the ampoule shortly before the measurement in accordance with the enclosed instructions. 6. This is due to the very small amount of sample (10 to 20 µL) that has to be injected. 2. The content of an ampoule is sufficient for 3 to 5 determinations. You can use a water standard with 1. Enter 0. The sample should be weighed either using a balance with a resolution of 0.g. with a Hamilton microliter syringe). Rinse a 10 mL syringe with approximately 1 mL of water standard. The error is minimized by rinsing and conditioning the syringe beforehand. To reduce the influence of the atmospheric moisture.3. Inject exactly 10. or with a 10. accurate results. METTLER TOLEDO XP205 balance) or with a 10 or 20 µL precision syringe (e. the whole content of the ampoule is completely drawn into the syringe.0 mg water/g for a titrant concentration of 2 or 1 mg/mL. Inject 1 to 1.

ethereal oils Petrochemical products: gasoline. it may draw water out of the needle!). creams. corn. dioxane. tar products. wipe off any drops that have adhered to the needle with two fingers (be careful if you use a paper towel. Always add each sample in exactly the same way. However.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. Do not warm the syringe. emulsions Petrochemical products: crude oil. Adjust the plunger to exactly 10. caramel. if it is absorbent. beverages Cosmetics: soaps. lay it down on the adapter and empty it completely. kerosene Pharmaceutical products: ointments. fatty creams Waxes. After setting the volume. amount 100% Samples Solvents: toluene. Solvent Methanol Max. You can get rid of any bubbles in the syringe by expelling the water rapidly. transformer oil. alcohols. Insert the syringe through the 1 mm hole of the three-hole adapter. suppositories Sugar products: jelly. ester Organic products: urea. the largest part of the solvent mixture must always be an alcohol (most preferably methanol) to ensure that the Karl Fischer reaction is strictly stoichiometric. potato chips Chloroform Decanol Octanol Hexanol Dodecanol Toluene Formamide 70% 50% 50% 50% (30%) 37 . massage oil.3. It is possible to determine the titrant concentration with water in all the solvents commonly used for Karl Fischer titration. to avoid touching the glass part. hydraulic oil. Only freely available water undergoes reaction with the Karl Fischer reagent. the sample must release water completely. salicylic acid Foods: honey. You should always observe the following points when determining the concentration with a 10 µL syringe: Precondition the 10 µL syringe for approximately one hour by filling it with water. - 4. All the screws in the syringe must be tightened securely. 2. yogurt. noodles.0 µL. fat Oils: edible oil. Always use a syringe with a long metal shaft. jelly bears Starch products: flour. You can use mixture of solvents to achieve complete dissolution. Hold the syringe at right angles directly in front of your eyes to read off the value.5 The solvent To determine the water content in a sample. diesel oil.

The solvents that are used should contain as few water as possible (< 100 ppm). 2. If acidic or basic samples are titrated. i.g. This will lead to incorrect results. In this case. 4.salicylic or benzoic acid for basic samples. buffering agents are first added to the solvent to ensure that the titration is quick and without side reactions: . 38 . the water will no longer be completely released.6 Dissolving capacity of the solvent The dissolving or extraction capacity of the solvent is a crucial factor in Karl Fischer titration. formamide effectively extracts water from starch products. The titrator accumulates the total water amount continuously during titrations and reports "Solvent capacity exhausted" as soon as the specified value is exceeded. The Compact Line KF titrators are able to monitor the solvent capacity: the user can define when the solvent should be replaced by specifying the usable life. and . the titration of subsequent samples will then be very slow. Sugar is the only type of sample that dissolves in formamide.e. or by indicating the maximum number of samples to be titrated.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. it is necessary to replace the solvent timely. The amount of formamide at 50 °C should not exceed 30%.imidazole is used for acidic samples. The extraction capacity can be improved by increasing the temperature (e. or the stoichiometry of the Karl Fischer reaction will change and the results will be wrong. you must replace the solvent timely. which may be completely expended if you titrate a large number of samples with high water content. Once again. The solvent for the two-component reagent contains SO2. or the titration will take too long and titrant will be wasted. Therefore. starch products will not dissolve in it. On the other hand. 50°C). the amount of water in mg which has been titrated. 3.3. too low water content. If exhausted.

the most common source of error. The sample must be representative. the solubility of water in the sample can be increased using a solubility promotion agent such as 2-propanol. and thus air moisture can penetrate the plastic and absorbed by the sample. It floats on the surface or sinks to the bottom.e.2 Storing the sample After you have taken the sample. If you have to store the sample. it must contain the same average amount of water as the material as a whole. you will no longer be able to determine its true water content. you should take into account the following points: 1.g. 5. water may be separated from the sample if it is left to stand for a long time. The sample should be taken quickly to exclude. or at least minimize. If the water content of a sample changes during sampling due to moisture being absorbed or desorbed. In such cases. 39 . This can happen when a sample cools and the water solubility is decreased. rinse the bottles two or three times with the sample beforehand.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5 Sampling 5. Heterogeneous water distribution in samples: In non-polar liquids.1 Taking the sample When taking samples for water determination. With liquid samples. i. "An analysis cannot be better than the actual sample!" When sampling. the sample should be larger the more heterogeneous the distribution of the water. oils. such as butter. Hygroscopic solids may exhibit higher water content on the surface than inside if they have absorbed atmospheric moisture during storage. which cannot be mixed as thoroughly as liquids. the water is not uniformly dispersed. With liquid samples that do not dissolve water such as oils. Substances with very low water content: Substances with a very low water content are frequently extremely hygroscopic. 3. 2. Liquids of this type must be thoroughly mixed (by shaking) before a sample is taken. keep it in a tightly sealed bottle: Glass bottles are preferable to plastic bottles because plastic is not completely gastight. In the case of non-polar solids. 4. you must be extremely careful to exclude atmospheric moisture . e. 5. The sample must therefore be taken very quickly and with a syringe or a spatula that is absolutely dry. the lower the amount of moisture. Use a bottle with an optimum volume for the amount of sample: the smaller the gas space above the sample. you should determine its water content as soon as possible. the absorption or release of moisture. Use sample bottles with small openings to minimize the ingress of moisture. Use bottles with a septum stopper for liquids of very low water content.

5 to 2 mg water per sample. the amount of sample should require a titrant consumption between 30 and 70% of the nominal burette volume.0 5000 0.05 mg water per sample with a titrant concentration of 1 mg/mL. For optimum accuracy with determinations in the range from 1 ppm to 1% water. Under optimum measurement conditions. and the required accuracy and precision. This corresponds to 0.5 mg water per sample for a 5 mL burette with a titrant concentration of 5 mg/mL.0 1000 1 1.0 10000 = 1% 0.1 to 0.4 500 2 1.5 to 17. because the absorption of atmospheric moisture during sampling or sample addition becomes less important.1 to 0. As a rule of thumb. and the following minimum sample sizes should be used: Water content Min. 10-50 μg water can be detected if the demand for repeatability is not too high. the accuracy increases with the amount of sample.01 10 8 0. approx. For a more accurate determination of water traces (10 ppm to 1000 ppm) by volumetric KF ttiration. This corresponds to 7.0 For volumetric titrations. because the absorption of air moisture during sampling and sample addition becomes less important. the accuracy is improved if larger sample amounts are used.2 1. a KF titrant with a lower concentration (1 or 2 mg/mL) has to be used. A titrant consumption of 0.3 Amount of sample The amount of sample used depends on • • the expected water content.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5.05 mL is thus still acceptable when using a 5 mL burette. If a high level of accuracy is required.1 mg water per sample. Water content determinations below 1000 ppm are not required to be quite as accurate: a relative standard deviation srel of 1 to 5% is generally considered as acceptable for such values. In general. For coulometric analyses.25 100 4 0. it is recommended to use the minimum sample size given in the following table: Water content Min. Repeatable results can be obtained even with 0. sample size [ppm] [g] 10 8 50 7 100 5 200 4 500 3 1000 2 40 . sample size Amount of water [ppm] [g] [mg] 1 10 0.08 50 5 0. the optimum amount of water is in the range from 0. the optimum amount of water is approximately 10 mg per sample.1 1.

The intersection point of this line with the "Amount of sample" scale represents the recommended amount of sample to be used. 1 mg for coulometric KF) or the recommended range The optimum point is connected by a straight line to the expected water content. Procedure: • • • Note: Start from the optimum point (10 mg for volumetric KF.METTLER TOLEDO Good Titration PracticeTM in KF Titration Determination of the amount of sample for a water content in the range from 1000 ppm to 100% Principle: The recommended sample size can be determined as a function of the expected water content for optimum KF analysis. Logarithmic scale! 41 .

an optimum sample weight range is recommended.METTLER TOLEDO Good Titration PracticeTM in KF Titration Example: Expected water content: Optimum amount of water: Optimum sample amount: 5000 ppm 10 mg/sample 2g The Compact volumetric and colometric KF titrators support the user with a sample size calculation routine. which is accessible in the online titrations screen: Dependent on the expected water content. 42 .

Store the sample in a bottle with a septum stopper to avoid moisture absorption from the air. Fill the 5 or 10 mL syringe with sample after removal of the piston. suppositories b c Liquefy the sample in an oven at approx. The following procedures are suitable for the different types of liquid samples: Sample characteristics High water content Low viscosity Examples perfumes. Possibly warm the sample slightly to lower the viscosity.1 Liquid samples When adding liquid samples. Rinse a 10 mL syringe 2-3 times with the sample Inject the sample using a 1 mL or 10 mL syringe through a septum cap. alcoholic beverages methanol. 43 . especially with samples of low water content. toluene. silicone oil. you must take suitable precautions to prevent atmospheric moisture from being absorbed. benzene glycerol.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6 Sample addition 6. The syringe is heated together with the wax. mineral oils massage oil Procedure Inject the sample into the titration vessel either through a septum (KF coulometer) or through the needle hole in the three-hole adapter (volumetric KF titrator) using a 1 mL syringe with needle. 50 °C and fill it into a syringe. edible oils hexane. Low water content Low water content Hygroscopic Viscous Very viscous ointments. This prevents the sample from solidifying in the syringe during the weighing. hydraulic oils. yoghurt. In the case of a volumetric Karl Fischer titrator. In the case of a volumetric Karl Fischer titrator. aqueous emulsions. Inject the sample using a 5 or 10 mL syringe with a thick needle into the titration cell. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. paraffin. honey a Waxy candle wax. Inject it into the cell using a wide-bore needle. creams. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. ski wax.

use bottles with a septum stopper and pressure equalization. Air flows through the molecular sieve into the bottle when you take a sample aliquot. the drop will adhere to the septum. Withdraw the plunger and rinse the syringe with the sample by shaking it. If the sample is hygroscopic or has a low water content (< 1000 ppm). Start the titration method by pressing the <Start> button Inject the sample into the titration cell through the septum stopper. – – – – – – – – – – 44 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Taking samples from a bottle with septum stopper After several samples have been taken. Enter the sample size in the titrator or transfer it automatically. a vacuum develops in the bottle with septum stopper and it will no longer be possible to take a sample aliquot. Withdraw the plunger so that the drop at the tip of the needle is sucked back into the needle. Fill the syringe with sample and wipe the needle with a paper tissue. seal it with cotton wool and insert it into the septum bottle using a short needle. Fill a syringe without a plunger with molecular sieves. To avoid this. Replace the syringe with the remaining sample on the balance and back weigh it. Place the syringe (upside down) in a beaker on the balance pan and tare the balance to "0". Otherwise when the syringe is removed. Empty the syringe (into the waste bottle) and repeat the rinsing two or three times. Start the titration. you must aerate the bottle with dry air (equalize the pressure). Sample addition of liquids with the back weighing technique – Fill the syringe to a quarter with sample.

The sample should be quickly weighed and added to minimize air exposure. thus. Finely powdered Dusty Finely powdered with very low water content Soft – Use a weighing boat with an attached flexible tubing to add the sample: it prevents the sample from adhering to the wall of the titration vessel or to the electrode. chocolate. pulverize less hard samples in a mortar. about 50-100 μg water enter the anode compartment. fatty e. this would lead to an error of 5% to 10%.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6. jelly bears. For instance. it is necessary to warm up such samples to room temperature in a closed vessel before weighing. – Add the sample with a weighing boat. coarse-grained samples in a closed. salts. e. cooled analytical mill. other methods have to be used for the determination of low water content by KF coulometry in solid samples: • • • External extraction External dissolution Drying oven On the other hand.g. e. With an optimum sample size of 1 mg water/sample. 45 . crystalline samples: Weighing boat – Grind hard.g.g. salicylic acid. Hard. almond paste: Cut into small pieces with scissors or a knife and add the sample with a spatula.g. cellulose powder: – Either weigh the sample in a dry box or extract it externally. jellied fruits. solid fat: – Grate the product and add the sample with a spatula. Sample characteristic Brittle Hard/soft Pourable Procedure e.when the titration cell is opened to add the sample. it should be added under the same conditions as it was transported and stored.2 Solid samples It is not possible to directly titrate solid samples using KF coulometry . depending on the ambient humidity. If possible. the storage of samples in a refrigerator may cause water to condense. in a volumetric KF titrator solids can be directly transferred into the titration vessel. For this reason.

50 °C and fill them into a syringe. Weight of solid samples with the back-weighing technique Weigh the sample in the weighing boat. fatty. suppositories: – Liquefy the samples in a drying oven at approx. – Add the sample with a spatula. Tare the balance to zero. sugar products – The METTLER TOLEDO Visco-Spoon™ simplifies the handling with creamy samples since it can be directly mounted into the titration stand.METTLER TOLEDO Good Titration PracticeTM in KF Titration Soft. butter. paraffin. Enter the weight in the titrator or transfer it automatically. ski wax. because the water is released if it is pressurized Waxy e.g. This prevents the sample from hardening inside the syringe during the weighing process Creamy Highly viscous e. Add the sample into the titration vessel. Back-weigh the empty weighing boat. Do not use a syringe. The syringe is heated up together with the wax. - 46 . candles. The water content is often lower atthe surface than inside the sample. chocolate cream. edible fat: – Homogenize the sample well: the water is heterogeneously distributed. margarine. Use a weighing boat with attached flexible tubing if necessary.g. honey. inhomogeneous e. Start the titration.g. to prevent the sample from adhering to the vessel wall or to the electrode.

e. This is not the case with solids if the water is bound as. fruit juice extracts. solid fat: Grate the product. sausage.g. minerals. brittle Viscous Hard. grain.g. The following methods are available: Sample characteristic Very hard Procedure e.g. e. then reduce it further with a homogenizer in an external solvent. it is necessary to crush insoluble solids in order to gain access to the trapped water.g.g.g. meat. Fibrous natural products Suspensions 47 . e. chocolate.g.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7 Release of water from the sample Karl Fischer titration is only possible if the water in the samples is freely available. jellied fruits. in plants) Water Example: Sugar. e. e. brittle Moderately hard.g. vegetable juices: Reduce with a homogenizer. almond paste (“marzipan”): Cut into small pieces with scissors or a knife. berries: Reduce with a homogenizer in an external solvent.: • • • • entrapped water water of crystallization (salts). hard salts: Grind in a closed. e. Sample preparation Water: Example: Biological samples First of all. fatty Mince the product. dried fruit and vegetables. suitable sample preparations and special Karl Fischer methods are necessary to release water in these samples. organic salts. coffee beans: Crush in a mixer. inorganic salts. water adsorbed on surface capillary bounded water (e. fatty Soft. crystalline products: Pulverize in a mortar. pharmaceuticals Water Example: Food Example: Gypsum (Ca2SO4 * 2 H2O) Thus. e.g. noodles. cooled analytical mill.g. e. cheese: Hard.

METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.5 8.8 Solvent Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol 48 .1 4.4 0. grinding the sample additionally with a built-in homogenizer (see photos below).1 Internal extraction Internal extraction is suitable for insoluble solids that release water quickly when crushed: – – Add the crushed samples into the titration vessel. Thermostatable vessel High–speed homogenizer Examples: Sample Flour Potato chips Ground hazelnuts Chocolate Instant coffee Dried chives Dried tarragon Aspirin Sweetener tablets Optical bleaching agent Result / % 12.4 1.2 1. e. You can speed up the extraction of water from the sample by • • In many cases.9 0.3 2.8 1. sugar. using either methanol or a mixture of it as the solvent.g.4 1. potato chips.9 0.5 1.8 1.0 1. etc.1 mg/pc 3. the homogenizer eliminates the need to use auxiliary reagents such as formamide with.3 1.9 srel / % 0.0 7.8 4.1 1. hazelnuts. heating the solution with a thermostating titration beaker. Water is then extracted providing the mixing time defined in the titration method is sufficiently long.

METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. Briefly. sugar and starch products for sugar (surface water) The organic solvents most commonly used are: • chloroform The external extraction is carried out in four steps: Step 1: Blank value determination of the extraction solvent Solvent in septum bottle Take a solvent aliquot Water content determination of solvent = blank value B - The water content of the solvent must be much less than the one of the sample. shaking bath) placing the solution in an ultrasonic bath for a certain time or reducing the sample further with a built-in homogenizer. edible fat) for natural substances (almonds. butter milk. methanol decanol / octanol formamide for insoluble organic solids for fatty and dairy products (butter. curry) for dehydrated products for sugar (total water). pepper. In particular. 350 ppm) and toluene (max. the finely crushed sample is added to a solvent with very low water content and is left to stand until the water has been released from the sample. Provide sufficient solvent for the blank value determination so that enough solvent is available for the extraction. Pay attention to the water capacity of chloroform (max. 600 ppm). 49 .2 External extraction External extraction is suitable for insoluble solids that release water only slowly when crushed as well as for samples with an extremely inhomogeneous water distribution. The extraction of water can be improved • • • by shaking the solution (mechanical shaker. water is extracted from the sample by means of a defined quantity of solvent of known water content.

For the extraction of tablets. the smaller the relative error because the total error is calculated with respect to the sample size. Add a sufficient amount of sample. A dilution factor of 10 . the addition of dry quartz sand has proven useful for improving and speeding up the extraction. The larger the sample. - 50 . A mechanical shaker is normally used because the extraction time is often long (at least two hours or overnight). or use an ultrasonic bath with heating.20 is normally used. Shaking is the method generally used for extraction.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 2: Weigh in solvent and sample Weigh solvent in = msolv Add sample Weigh sample = mext - Cut the sample into small pieces so that it releases its water more quickly and efficiently. Step 3: Extraction - Shake. or use a homogenizer.

1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m . % or ppm). 51 . Water content of the supernatant extraction solvent (% or ppm) %: C = (VEQ*CONC-TIME*DRIFT/1000)*0.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 4: Allow settling. take an aliquot and titrate Allow to settle Take an aliquot of the extraction solution Titrate sample The following equations are used to calculate the water content of the extracted sample: ⎛ msol B ⋅ msol ⋅ ⎜C ⋅ − ⎜ mext mext ⎝ ⎞ ⎟ ⎟ ⎠ For % : R (%) = 100 100 − C For ppm : 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − R( ppm) = 6 ⎟ mext ⎠ 10 − C ⎝ mext Water content in the sample P (% or ppm). R: C: B: msol: mext: m: Note: Blank value (water content of the solvent. Amount of solvent (g) Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) The detailed calculations which lead to these formulas are given in the appendix.

8 54.5 9. The solvent blank is determined directly from the method running in standby by pressing the ‘Start blank’ button.4 4.4 0.4 0.6 61.METTLER TOLEDO Good Titration PracticeTM in KF Titration Examples for the external extraction: KF Coulometry Sample Result / ppm srel / % Extraction solvent Sucrose (surface water) 72 4.9 11.5 0.4 0. The weight of the solvent (msol).6 0.5 Decanol:formamide:methanol 8:2:1 Decanol:formamide:methanol 8:2:1 Decanol:formamide 1:1 Decanol:formamide:methanol 8:2:1 Methanol Methanol Formamide There is a dedicated KF method type ‘External Extraction’. the weight of the sample (mext) and the weight of the aliquot of the supernatant solution containing the extracted water (sample size m) is entered into the respective sample data fields: 52 . The METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator are available with optimized method parameters for immediate execution.2 Chloroform Volumetric KF Titration Sample Result / % srel / % Extraction solvent Cheese Liver sausage Mustard Chicken broth Tobacco Wool Acrylic paint 27.3 0.3 0.6 72.

Chloroform. Note: 1. “External extraction”) in the method function “Calculation”. 2. by selecting the appropriate calculation (i. the formula is automatically given. The amount of sample should also take account of the absorption capacity of the solvent. reaches the saturation limit for water already at 350 ppm! 53 . The amount of sample should be sufficiently large to ensure that the amount of water in the sample is significantly greater than that in the solvent prior to extraction. 3. in order to maximize the extraction effect and ensure that the difference between the water contents before and after extraction is as large as possible. for instance.e.METTLER TOLEDO Good Titration PracticeTM in KF Titration The equation for the calculation of the water content of the extracted sample is predefined in the calculation method function. In particular. The water content of the solvent should be as low as possible.

1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m B: msol: mext: m: Blank value (water content in % or ppm) of the solvent. only the calculation method function has to be adapted to by selecting the corresponding calculation from the list of proposed results. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) 54 .2 10.2 1. waxes and suppositories Example: Sample Result / ppm srel / % External solvent Sucrose (total water) Naphthalene Phenol Salicylic acid Contact adhesive (“Rubber cement”) 533 35 174 116 278 4.8 2.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % AND ppm: R: C: Water content in the sample P (% or ppm) Total water content (sample + solvent). The following solvents are commonly used: • • • • methanol formamide chloroform toluene for organic solids for sugar products for petroleum oils and adhesives for tar. External dissolution is suitable for soluble solids with an extremely inhomogeneous water distribution. ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%. %: C = (VEQ*CONC-TIME*DRIFT/1000)*0.9 5. The dedicated method type ‘External Extraction’ and the METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator can be used as templates.3 External dissolution External dissolution is defined as the complete dissolution of a sample in a defined amount of solvent of known water content. the addition of methanol is not necessary. or with a very low water content. in % or ppm.3 formamide methanol methanol methanol chloroform The method corresponds to external extraction except that the sample dissolves completely in the external solvent. or with a high water content Pure solvents can be used to dissolve the samples.

7. biological tissue.4 Lyophilized substance in septum bottles The extremely low water content of freeze-dried substances (e.20 mL of anolyte titrated to dryness into the syringe. because a large sample amount leads to a too long titration time. Determine the weight by back weighing. Since you are able to work with larger amounts of sample when working with this technique. 4. 7. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell.METTLER TOLEDO Good Titration PracticeTM in KF Titration To obtain accurate results a large sample amount is used for substances with an inhomogeneous water distribution. the sample is previously diluted through external dissolution to be able to titrate a larger sample aliquot. You should therefore proceed as it follows: Take an aliquot of anolyte Inject it in the septum bottle Shake Take aliquot and titrate Procedure: 1. KF coulometry is not suitable for samples with water contents of 10-100% because a very small amount of sample would have to be used. weigh it and inject it into the titration cell. If the solid has a low water content (<200 ppm). Determine the weight of anolyte injected by back weighing. Draw an aliquot into the same syringe again. On the other hand. the blank value correction is too large compared to the amount of water in the sample. 5. Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. foodstuffs) in septum bottles means that external extraction or external dissolution as described in the previous sections are not recommended. Thus. serum. the error as a result of opening the titration stand will be between 10 and 30 µg. Draw 10 . Rinse the syringe two or three times in this way. Direct titration is not suitable. If 1 g of sample has a water content of 100 ppm (= 100 µg) for instance. 6. this error is reduced. the error obtained by direct titration if the titration stand is opened to add the sample is too large. 3. 2. In fact. and too much titrant is consumed.g. Remove approx. 55 . weigh it and inject it into the septum bottle.

Since ¼ of the total amount was injected. the water amount in the septum bottle is 4 times larger. 3. In this way. 2. the final result must be multiplied by 4 (factor f = 4). Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. Alternative procedure: 1. zero must be entered for the blank value (B). 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell. Draw exactly 5 mL from the septum bottle into the same syringe again and inject it into the titration cell. Rinse the syringe two or three times in this way. because the anolyte titrated to dryness has a blank value of "0". If you know the lyophilized sample amount in the septum bottle. Remove approx. Thus. 6. 4. then you can additionally calculate the result can be given in ppm. With a standard method calculation and calculate the water amount in µg. 7. The accuracy of a plastic syringe is enough. 56 . 8. The water amount in µg is determined. Draw exactly 20 mL of anolyte titrated to dryness into the syringe and inject it into the septum bottle. neither the calculation for the external extraction nor for the external dissolution are needed for this procedure using the volume instead of the mass. 5.METTLER TOLEDO Good Titration PracticeTM in KF Titration If the sample is completely dissolved: use the method type “External extraction” and the calculation for the "External dissolution" If a suspension is formed: use the method type “External Extraction” and the calculation for the "External extraction" Note: In both cases.

57 . to prevent the gas from flowing into the titration vessel.Turn the three-way valve. depending on the water content of the gas.Adjust the gas stream to a constant flow rate with the control valve: 50 to 200 mL/min. water-free absorption liquid in which CO2 itself does not dissolve. .With sample vessels the gas amount gas can be determined by differential weighing. time" and a "Delay time" of e. The water contained in the gas is then absorbed by the liquid and can be determined by means of Karl Fischer titration in a process similar to external extraction.5 Determination of water in gases To determine the water content of gases. Three-way valve Flow meter Gas Control valve The flow rate has to be constant to determine the volume necessary to calculate the water content: gas volume = gas flow rate x time. The gas must be directed through a water-dissolving.g.Add a sufficient amount of buffer solution into the titration vessel to determine the water content of acid gases such as e. .CO2 gas can not be titrated directly since iodine reacts with CO2. . .As soon as the drift is stable again. .Purge the system with the gas before you start the determination. evaporated methanol lost in the gas stream must be replaced depending on titration time and number of determinations. The water content in ppm is calculated by entering the volume and the density.g. Sampling/sample addition . . start the titration and reset the three-way valve to its original position in order to direct the gas into the titration vessel. If not.When titrating large quantities of gas in the same solvent. Notes . hydrochloric acid. Determination .Calculate the volume from the time and the gas flow rate. 600 s as termination parameters. . . you should titrate the gas sample directly from the source.If possible. to ensure that the titration is terminated after the maximum time.Purge the sample vessel and the tubings thoroughly beforehand with the gas. you must fill the gas either into special gas sample tubes or into small steel cylinders.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.Select "Max.Stop the gas flow after 1 to 2 mL titrant has been consumed. . . the gas must be directed through the titration vessel for a defined period of time.

6. the residual moisture in the purge gas should be less than at least 10 μg/L (for coulometric determination) and 20 μg/L (for volumetric KF titration) in order to obtain accurate and repeatable results.1 bar (cf. Experiments with various gas flow rates yielded the following results: Gas flow rate Recovery [mL/min]: [%]: 108 99. the purge gases must be first dried before entering the KF oven.4) A gas stream of approx. cause side reactions with the Karl Fischer reagent.5). 150 mL/min is ideal for DO308 and 70 mL/min for Stromboli (automated KF drying oven. and the amount of water is determined. e. chapter 7. 7. Thus. 58 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. If you use air for organic samples.6.6.: o o air with 50% humidity: approx. cf.2 Purge gas Air contains oxygen. If you use nitrogen from a gas cylinder. or 2.1 - The recovery rate is clearly decreasing with increasing gas flow rate. for accurate results do not select a too high gas flow rate. The water is transferred to the titration cell in a current of dry inert gas (purge gas).7 500 97. The purge gases commonly used contain moisture. chapter 7. 11 mg/L nitrogen gas from a cylinder: 1. For Karl Fischer titration.g. inorganic samples.6. that release water very slowly.5 . the oven temperature should not exceed 160 °C.4 – 8. Air should therefore only be used for non-oxidizable.9 166 99. you should use a two-stage pressure regulator so that the final pressure is in the range 0. causing the water in the sample to vaporize.6 Determination using the drying oven This method is suitable for solids and liquids that 1. which could react with the sample at higher temperatures. 7.1 Principle The sample is heated in an oven.0 mg/L Therefore.

whereas molecular sieves requires temperatures up to 300 °C. In order to avoid the latter you may also use the minimum time as termination parameter. in contrast to other desiccants.e. deactivate the drift stop).e.50 µg H2O/L 15 – 20 µg H2O/L 50 – 60 µg H2O/L 5 – 10 µg H2O/L 10 – 15 µg H2O/min 8 – 10 µg H2O/min 3 – 4 µg H2O/min 10 – 12 µg H2O/min 1 – 2 µg H2O/min You can use the following desiccants to dry the purge gas: – – Molecular sieves are the best drying agent as far as residual moisture is concerned.6. the titration starts and the released water is continuously titrated.METTLER TOLEDO Good Titration PracticeTM in KF Titration Several agents are available to dry the purge gas: Method Residual moisture Residual moisture for 200 mL/min gas flow rate (drift) Sulfuric acid. especially methanol. you should set the maximum titration time as the termination parameter (i. there are two types of anolyte solutions: 59 . 100% Phosphorous pentoxide. Passing the gas stream into the titration cell causes the anolyte (in the KF coulometer) and solvent (generally methanol in KF volumetric titrator) to vaporize.e. With some samples the drift at the end of the titration is significantly higher than the initial drift. they are rapidly exhausted. i.3 Procedure There are two different methods to perform a KF titration with the drying oven: 1. In such cases you should use the maximum titration time as termination parameter (i. This is caused by a slow release of the final traces of water or slow thermal decomposition of the sample. 7. 2. Method 2: The water is first vaporized and then titrated afterward During a defined long mix time.80 µg H2O/L 40 . Silica gel can be regenerated over night at 150 °C. Silica gel is appreciably better in this respect. The amount depends on the gas flow rate and the type of KF reagent present in the titration cell. deactivate the drift stop). In the case of KF coulometers. Method 1: The water evolved is continuously titrated After a short mix time (20 . all the water is vaporized and transferred to the titration cell. To ensure that the determination is repeatable. Silica gel and molecular sieves have the advantage that they can be regenerated. It is therefore recommended to dry the gas with a combination of silica gel and molecular sieves. At the end of the titration. The KF titration is then started. The short mix time is necessary so that a delayed vaporization of water does not lead to premature termination of the titration. but their water absorption capacity is low. The relative drift stop or the maximum titration time can be used as the termination criterion. Start off with the silica gel to absorb the bulk of the water and then use molecular sieves to reduce the residual moisture to a minimum.60 s). P2O5 KF one-component reagent Silica gel Molecular sieves 3 Å 50 . the vaporization is often very irregular.

Examples: Sample Result / ppm No. time 60 .METTLER TOLEDO Good Titration PracticeTM in KF Titration – Standard anolyte solutions containing methanol (e.g.2 4.200 mL/min. time Max.2 1. oven temperature 200 °C: approx. oven temperature 200 °C: approx.1 Briefly: The less methanol is vaporized.g. the recovery is not 100%. 3.4. there is a small loss of water. you should replace the anolyte lost through vaporization with new anhydrous methanol. time Max.7 99. Make sure that the level of the anolyte does not fall below that of the catholyte (higher drift!). i. i. The procedure for the determination of water content is described in the operating instructions. fibers) or with samples of low water content. 1 mL/hour – From time to time.e.8 6.2 99. Due to the vaporization of the methanol. time Max. 7. as well as a gas flow meter.9 9.5 mL/hour Anolyte containing ethylene glycol. and the better the recovery.95 98.5 190 280 140 300 300 200 15 10 15 20 10 15 Max. The recovery therefore depends on the amount of methanol vaporized and the method used.4 Manual Karl Fischer drying oven The METTLER TOLEDO DO308 drying oven can be operated in a temperature range from 50 to 300 °C. As an example data from coulometric determinations are indicated here below: Method Anolyte Gas flow rate Recovery / % 1 1 2 2 Coulomat AG Coulomat AG Oven Coulomat AG Coulomat AG Oven 166 mL/min 183 mL/min 166 mL/min 106 mL/min 99.9 2.g.5 .e.200 mL/min. of samples srel / % T /°C Time/min Comments Polyamide Polyethylene Motor oil Cement Cooking salt Carbon black 5547 68 842 8200 360 3583 6 6 6 6 5 5 0. time Max. the faster the water is titrated. time Max. This is particularly important with low-weight samples (e. dedicated anolyte to be used with a KF Oven (e.6. An air pump is available as an optional accessory. Coulomat AG or CombiCoulomat frit): Anolyte loss at 150 . It has a large glass sample boat capable of holding up to 10 cm3 of sample. The DO308 oven is equipped with a gas drying unit with two bottles for silica gel and molecular sieve. Coulomat AG Oven): Anolyte loss at 150 .

and/or replace the anolyte of the KF coulometer. Experiments using methanol as the solvent gave a recovery rate of 98% for a stream of 166 mL/min. Some samples have surface water that is lost as soon as the oven is purged with dry gas. start the titration so that the drift value is automatically entered. Always start the titration before you place the sample in the oven to ensure that the correct drift value is adopted by the method (online drift). in volumetric KF titration the methanol loss is approx. Then. The drift should be 5-10 μg H2O/min at a gas flow of 150 mL/min. evaporated solvent does not condense in the drying tube. 10. bent drying tube. Coulometer KF: The internal drying tube of the generator electrode has to be replaced with an external. 5. For the same reason.55% or VWR/VWR/MERCK water standard KF oven 1%. purge the "cold zone". 3. To check the performance of the titrator/drying oven system. For instance. 6. Close the stop cock and purge the "hot zone". you may use the SIGMAALDRICH HYDRANAL® water standard KF oven 5. If the drift is constant. Add the sample through the tapered joint and slide the glass boat with the sample into the oven: Guide rod with magnet Slider Glass sample boat 8. Here a short mixing time (15 to 60 s) or the minimum titration time should be defined to prevent the titration from being terminated too early. 4. 3. This leads to a too low result. The evaporation is reduced by adding ethylene glycol (higher boiling point) to a maximum solvent ratio of 20-30%.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments: 1. Some samples require some time before water starts evaporating. do not select the parameter "Auto start". you should proceed as follows: 7. replace the silica gel and molecular sieves of the gas drying unit. and does not drop into the cathode compartment/ titration cell. This can happen when the titration is started only after complete evaporation. 61 9. 2.7%. the recovery increases to 99. If several determinations are performed in the same solvent. If the water is titrated as soon as it begins to evaporate. Set a gas flow rate of 150-200 mL/min. . In such cases. Open the stop cock. If the drift is higher than 15 μg H2O/min.5 to 4 mL/h for an oven temperature of 200 °C and a flow rate of 200 mL/min. the evaporated solvent lost in the gas stream has to be replaced. A large amount of evaporated water cannot be fully absorbed by the solvent.

2. 3. Besides 14 places for glass sample vials. 62 . The drying oven can be operated in the temperature range from 50 to 300°C. The purge gas flows through the sample vial and the water vaporized is transported via the transfer tube into the titration cell of the coulometer. including the oven temperature. STROMBOLI is completely controlled by the titrator: all the parameters for the determination. The blue rubber cap seals the sample vial tightly against the oven. STROMBOLI offers one fixed place on the sample rack for an empty sample vials in order to determine the drift value.6. the lift is moved downward and gravity facilitates the removal of the sample vial from the oven. The oven heats the sample to the set temperature. while a glass tube pierces the aluminum foil cover. are included in the titration method. The sample vials are moved upward into the oven by a lift.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.5 STROMBOLI automatic oven sample changer The METTLER TOLEDO STROMBOLI oven sample changer is a drying oven for automatic Karl Fischer titration with the KF Compact Volumetric V30 and Coulometric Tititrators C30 as well as with the Titration Excellence Titrators T70 and T90. After the analysis. 1 During a sample series: 2 3 1.

Drift determination: The drift determination is performed with an empty vial on the first position of the sample rack.METTLER TOLEDO Good Titration PracticeTM in KF Titration Sample vials: Rubber cap Aluminum foil Sample vial The glass sample vials have a large volume (up to 25 mL). The sample vials are sealed with self-sealing aluminum foil and a rubber cup. the moisture in the empty sample vial has first to be removed. This is particularly important with light samples (e. fibers) or with samples of low water content. This takes 10-20 minutes as can be seen in the following diagram: 63 .g. The drift value is defined as the moisture entered into the titration cell by the purge gas. To determine the drift value accurately.

Important: After a blank value determination. the vial used no longer has the same properties as the "fresh" sample vials.300 μg water. the method contains a so-called sample loop. and thus the moisture adsorbed on the glass walls is not always the same.METTLER TOLEDO Good Titration PracticeTM in KF Titration Blank value determination: The blank value is the amount of water contained in an empty sample vial (i. This means that the stored drift value of the previous determination will be used. you can enter the number of samples the series includes for each loop. Nevertheless. the silica gel and molecular sieves in the bottles of the gas drying unit can be replaced. the moisture content is somewhat lower. If. The blank value should be determined before each series because the humidity can change. you can check whether the drift is constant and the new drift value can be used for the next series. At the start of the method. With rapidly changing. The loops run through one after the other and the samples are processed sample for sample. i. a drift determination should still be performed at least once a day in order to check whether the drift is too high (e. By performing a drift determination at the end of the series or between several series. In this case. There are dedicated METTLER TOLEDO multi-loop methods available in the V30 (M313) and in the C30 (M396).g. Multiple sample series at different temperatures Several series can be started on the same sample turntable – even at different temperatures. It is therefore not necessary to perform a drift determination before each series. etc. for example. as well as the anolyte in a coulometric analysis.e. different plastic samples have to be analyzed.e. If the maximum titration time is used as termination criterion in the method -which is what we recommend. and the adsorbed moisture on the glass walls of the vial) minus the amount of water due to the drift (i.e. To determine the blank value as accurately as possible. 64 . > 15 μg H2O/min). moisture in the sample vial. The blank value can also vary as a function of temperature.e.the analysis times for the determination of the blank value and for each sample are the same. the last sample vial that was baked out remains in the oven until the temperature has stabilized at the temperature of the next loop and the drift is low and stable. If the temperatures of successive loops are different. Thus. whose optimum bake-out temperatures differ. the blank value determination also takes the actual drift into account. several blank value determinations can be performed one after the other in the same loop and the mean value calculated from the results. they can be measured at different temperatures using the same method. For each series.) are always slightly different. a blank determination can be performed between two sample loops. In the same way. the moisture in the air present in the vial. Performing the drift and blank value determination In general. The optimum blank value is in the range of 70 . drift value x time). The first sample of the next loop is then transferred into the oven and the water determination begins. The new blank value is automatically used for the blank correction. one with the same properties as the sample vials into which the samples have been filled in). suboptimum conditions. These method templates are based on a dedicated KF method type called ‘Stromboli’. the drift value can change with time. If this is the case. it is important to use a new sample vial for each blank value determination (i. a blank value determination should be performed before each series of samples since the ambient conditions (humidity. at the end of a series the blank value can be measured again and compared with the value determined at the beginning. gas flow. In this case.

The amount of moisture adhering to the glass surface of the sample vials strongly depends on how the vials were treated beforehand (cleaning. you can use SIGMA-ALDRICH HYDRANAL® water standard KF oven 5. evaporated solvent is not condensing in the drying tube. In this way. This valve shall be used especially if inert gas sources are used.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments on the operation with the STROMBOLI oven sample changer: 1. Set a gas flow of 40–60 mL/min. To check the titrator/drying oven system. 2. Therefore no precious inert gas is lost and no vacuum is applied to the system which may result in a back aspiration of the anolyte into the hot oven. KF Coulometer C30: The internal drying tube of the generator electrode has to be replaced with an external. toluene. This is necessary so that the KF solvent or anolyte is not aspirated into the hot sample vial if Stromboli is not properly shut down while it is still hot. These are partially vaporized (e. The delivery tube has a T-piece that causes a small leak flow. An optional 3/2 way valve which is automatically controlled by STROMBOLI can be used instead of the T-piece mentioned in 1. A special (longer) gas inlet glass tube is provided to bubble gas into the liquid. 4. Use the same vials for a sample series as well as for the blank value determination. motor oil) or completely vaporized (e. Vials that have undergone different treatment can show differences in the blank value of 50-150 μg water.g. drying and storage). 7. 3.55% or VWR/VWR/MERCK water standard KF oven 1%.g. since it provides a leak free inert gas stream during normal operation. and therefore it does not drop into the cathode compartment. see also list of results). bent drying tube. This test also serves to check the tightness of the oven and the connection tubing 65 . 8. 5. Allow sample vials that have been used or cleaned to stand overnight in the atmosphere for conditioning before starting measurements. you can not only determine solids but also liquid samples. A sudden shutdown of power immediately switches the valve in that way. This has a large effect on the blank value and thus on the result. that the inert gas stream to the gas source is closed and the system is ventilated with ambient air. With STROMBOLI. 6.

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

Examples:
Sample Result [ppm] No. of samples srel [%] T [°C]
Max.Time

[s]

Comments

Polylactic acid 0.5 g Polymer ABS-50 T 10014 3g Polymer ABS-50 F10014 2g Motor oil 1120/03 (AA) 2g

2589

3

1.1

160, air 190, N2gas 170, N2gas 165, air

--

Stir time: Max. time: rel. drift:

600 s 300 s 3 µg/min

736

5

1.1

300

Stir time: 900 s Delay time: 300 s Stir time: 900 s Delay time: 300 s Stir time: 60 s Delay time: 300 s Very slow evaporation, not faster with 180°C, above 180°C decomposition Stir time: 60 s Delay time: 300 s Very slow evaporation, above 180°C decomposition

1312

13

0.9

300

241 261

3 4

4.4 7.9

1500

Motor oil 1034/03 (AA) 1.5 g

426 438

4 3

2.7 4.5

180, air

1800

66

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

8 Measurement results
8.1 Resolution and detection limit
The following table indicates the theoretically smallest increments of current (KF coulometric) and titrant (Volumetric KF) which could be achieved by the instruments based on their technical specifications. Therefore, these are indicative values and they should be considered as such:
C20/C30 Compact Coulometric Instrument V20/V30 Compact Volumetric Titrator Resolution: 20’000 burette steps
5 mL burette: 0.25 µL c=5 mg H2O/mL: 1.25 µg H2O/step

Theoretical smallest increment

0.1 mC
Theoretical: Resolution:

(100 mA x 1 ms)
0.01 µg H2O < 0.1 µg H2O

Detection limit (limit of detection, LOD)

10 µg
Example: 10 g sample → determ. of 1 ppm Assumptions: - Current is used for iodine generation - Generated iodine is reacting 100% with water only.

50 x resolution
5 mL burette: 12.5 µL c=5 mg H2O/mL: 62.5 µg H2O Example: 5 g sample → determ. of 12.5 ppm

The theoretically smallest current increment that can be generated by the C20/C30 Compact Coulometers is 0.10712 mC which corresponds to 0.01 μg water. However, the achievable resolution of the instrument is in the order of less than 0.1 µg H2O, whereas the detection limit (also called “limit of detection”) is approx. 10 μg water per sample. Thus with a 10 g sample, 1 ppm water can be determined. For the V20/V30 Compact Volumetric instruments, the detection limit mainly depends on • • • The resolution of the burette drive, i.e. the max. number of steps which can be achieved by the stepper motor. the burette volume size; generally, a 5 mL burette is used for volumetric KF titration. The concentration of the titrant.

8.2 Measurement accuracy
The accuracy strongly depends not only on the technical specifications of the instruments, but also on the several factors that have been already mentioned in the previous chapters: 1. Sampling (including suitable storage, if necessary) 2. Sample treatment and preparation 3. Expected water content and selection of suitable instrument 4. Selection of optimum sample size 5. Condition of the KF reagents, i.e. fresh reagents, pre-titration, low drift value, … 6. Sealed titration vessel and tight tubing, 7. Condition of the indication electrode 8. Coulometry: condition of the generating cell 9. Parameter settings in the titration method etc. 67

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

To determine the closeness of agreement between the result of measurement and the true sample value, measurements can be performed either by titrating water standards or by titrating samples with known water content. The measurement accuracy depends on all the various factors described and explained in the previous sections. The crucial factors are optimum control as well as the water content and the amount of the sample.

8.3 Repeatability
The closeness of the agreement between the results of successive measurements of the same sample can be expressed quantitatively as the relative standard deviation, srel, given as %. With optimum sample amount and control, the following values can be obtained under test conditions for repeatability. The graph shows the relative standard deviation for different water contents. In general, the repeatability of a sample series becomes worse with decreasing water content. Note that for water content below 10 ppm it is not recommended to use a volumetric technique.

100% 10% 1% 1000 ppm 100 ppm 10 ppm 1 ppm

Coulometry
Not suitable for coulometry

Volumetry
srel < 0.5 %

srel < 0.5 %

srel 5 - 0.5 % srel 5 - 0.5 % srel > 5 % srel > 5 %
Not suitable for volumetry

In the following graphs, the relative standard deviation srel (%) of several series with different water content are given as a function of the sample size:

68

69 .0 Sample size (g) In both cases. A good repeatability is achieved the sample size is increased particularly for low water content values.METTLER TOLEDO Good Titration PracticeTM in KF Titration Relative standard deviation srel vs.0 5.0 3.25 0. Therefore. it is necessary to use the optimum sample size in order to achieve precise results. with decreasing sample size the relative standard deviation srel becomes worse.0 2. sample size for different water contents: KF Coulometry KF Volumetric Titration: srel (%) 6 110 ppm 5 330 ppm 4 720 ppm 3 2 1 0 0.5 1.

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Good Titration PracticeTM in KF Titration

9 Interferences
9.1 Effects of temperature
Temperature effects on the KF titrant The Karl Fischer titrants consist of approximately 90% methanol or ethanol. Their volume increases considerably if the temperature increases, and their concentration decreases accordingly. S. Eberius [3] specifies a correction factor of 0.0012 per degree Celsius for methanolic Karl Fischer solutions. According to ISO 760, a temperature increase of 1 °C causes a drop of 0.1% in the concentration. The titrant (in particular, the two-component KF solvent) may loose sulfur dioxide if the temperature rises. This causes bubbles to form in the titrant tubing, an effect which is worse the faster the rate at which the burette is filled. These titrators allow you to define the filling rate of the burette separately for each titrant, e.g.:
Temperature / °C < 15 15 – 30 > 30

Filling rate for one-component KF volumetric titrant / % Filling rate for two-component KF volumetric titrant / %

100 80

100 60

70 40

Titration at low temperatures You can perform Karl Fischer titrations at low temperature to eliminate undesired side reactions. The water content of peroxides, for example, can be determined at -40 °C. You must use the two-component reagent to do so, because the reaction rate of the onecomponent reagent is too slow at this temperature. Titration at high temperatures Increasing the titration temperature speeds up the dissolution of the sample or the extraction of the water from it, resulting in shorter titration times. Titrations at elevated temperature have proved particularly effective for foodstuffs, e.g. sugar, flour, potato flakes, hazelnuts, custard powder. The maximum temperature depends on the boiling point of the reagent (boiling point of methanol: 64 °C, boiling point of ethanol: 78 °C).

9.2 Side reactions
Side reactions that falsify the results can occur parallel to the Karl Fischer titration. There are mainly three side reactions that can affect the result: 1. Reaction with methanol, CH3OH Aldehydes and ketones react with methanol leading to additional water Esterification with carboxylic acids leading to additional water Ketones and aldehydes react with sulphur dioxide, a base and water (i.e. water is consumed) The reaction of iodine with e.g. oxides, hydroxides, carbonates, amines, ascorbic acid, and mercaptans leads to a higher consumption of iodine giving higher water content.

2. Reaction with water, H2O

3. Reaction with iodine, I2 -

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9.2.1 Reaction with methanol
Aldehydes and ketones: Methanol, CH3OH, reacts with aldehydes (R-CHO) and ketones (R-CO-R) to form acetals (CH3-CH(OR2)2 , and (CH3)2C(OR2)2 respectively, the latter also called ketals), as well as water: Formation of acetals:

CH3CHO + 2 CH3OH
Formation of ketals:

→ →

CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O

(CH3)2CO + 2 CH3OH
Solution: -

Use the special reagents for aldehydes and ketones with these substances (so-called K-reagents). They contain other alcohols than methanol. - Experiments have shown that the side reaction still takes place despite these reagents. Each time acetone is determined, for example, the drift is higher than before the titration: the larger the sample, the greater the drift increase. It is therefore recommend to perform the determination with a small sample amount and to replace the solvent after two or three samples. Esterification: Methanol, CH3OH, reacts under presence of strong acids (i.e. sulfuric acid) with carboxylic acids (R-COOH) to an ester (R-O-CO-CH3) and additional water:

R-COOH + CH3OH →
Solution: -

R-COO-CH3 + H2O

First neutralize the sample using a suitable base (imidazole) before KF titration.

9.2.2 Reaction with water
Another side reaction, the bisulfite addition, occurs with aldehydes and ketones in the presence of SO2. Water is consumed in the process. Bisulfite addition:

CH3CHO + H2O + SO2 + NR R1-CO-R2 + HSO3Note: SO2 + H2O = HSO3- + H+ Solution:

→ →

HC(OH)SO3HNR R1(R2)C(OH)SO3-

- Start the titration immediately after adding the sample. - Perform a fast titration by predispensing 90% of titrant consumption This causes the water to be titrated quickly, before any bisulfite addition can take place. The "Autostart" parameter allows for the automatic start of the titration as soon as the sample has been added and water is detected.

9.3 Reaction with iodine
The Karl Fischer reaction is a REDOX reaction with iodine as the oxidizing agent. Thus, iodine may also react with readily oxidizable samples. On the other hand, iodine can also be reduced by SO2 in some samples such as e.g. oxides. Both reactions cause additional iodine being consumed, giving a false higher water content.

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The following substances can react with iodine:
Ascorbic acid Boric acid, H3BO3 Disulfite, S2O5 2– Hydroxide, OH– Mercaptans, R-SH Peroxide, R-O-O-R Sulfite, SO3 Tin(II) salts
2–

Arsenite, AsO2 – Tetraborate, B4O7 2– Iron(III) salts Hydrogencarbonate, HCO3– Nitrite, NO2
– 2– 2–

Arsenate, AsO4 3– Carbonate, CO3 2– Hydrazine, N2H4, and its derivatives Copper(I) salts Oxides, e.g. CaO, MgO, MnO2 Silanols, R3-Si-OH Thiosulfate, S2O3 2–

Selenite, SeO3 Tellurite, TeO3

Solution: The Karl Fischer titration for the majority of these substances can be performed with the aid of the drying oven, or also by performing an external extraction.

9.4 Example: reevaluation of side reactions
The water content obtained is too high if side reactions previously described have occurred. This can also be the case if a drying oven is used, and the sample slowly decomposes. Nevertheless, the correct result can be reevaluated by graphical extrapolation. Example: Water determination in red polypropylene fibers.
µg water

250 °C 160 °C 120 °C

300 200
115 mg 640 ppm

100

0

5

10

15

20 min

The determination was carried out for a period of 20 minutes (max. time) with the drying oven set to 120 °C, 160 °C and 250 °C. The following results were obtained:

120 °C 1186 ppm

160°C 1442 ppm

280°C 1955 ppm

The volume-time curve clearly indicates the occurrence of a side reaction, which becomes faster with increasing the temperature. The "water content" increases with temperature. By reevaluation using the LabX® titration PC software the actual water content can be obtained by extrapolating the titration curve to time t = 0 min (green dotted lines). The content is 115 mg water; this corresponds to a water content of 640 ppm for a sample weight of 0.18 g. The extrapolated result was confirmed by an external extraction in methanol. In fact, the result obtained with this method was 610 ppm.

72

Replace anolyte Amount of sample too small . if possible increase amount of sample Wrong sample preparation and sample addition .Use smaller sample Long titration time.Homogenize sample. especially at low water content (< 1000 ppm) 73 . .Use t(max) as termination parameter .g.Increase end point Oven: water vaporizes very slowly and irregularly .Check whether titration stand is completely tight. drift stop as termination parameter.Increase value for rel. drift stop .Use higher oven temperature . Oven: . .Replace anolyte .Grease the tapered joints Moisture from cathode compartment and diaphragm . 1 mg water per sample is present.Lengthen vaporization time (increase t max) . increase t(max) Wrong control parameters . titration never ends Very long pretitration Poor repeatability Wet anolyte . Water distribution in the sample is not homogeneous .1 Coulometry Problem Possible causes and action to take Anolyte is not bright yellow but dark yellow to brown Drift is too high after the pretitration of a fresh anolyte .Replace silica gel and molecular sieve in the gas drying unit The drift remains too high during standby titration Drift is too high after the titration of a sample Side reaction with the anolyte .The repeatability is strongly dependent on suitable sample preparation and sample addition.Higher oven temperature .Replace molecular sieves and silica gel in drying tube .Clean the platinum pins of the measurement electrode with paper tissue .Measurement electrode is not plugged in .METTLER TOLEDO Good Titration PracticeTM in KF Titration 10 Troubleshooting 10.Use rel.Clean titration cell and generator electrode and dry at 50 – 80 °C .Use a different method Oven: water not completely vaporized . .Increase amount of sample to ensure that approx. e.Increase vaporization time.Measurement electrode is faulty Titration stand not protected against moisture .Level of anolyte should be higher than that of the catholyte .Add a small amount of one-component KF titrant to the catholyte.Check whether titration stand is completely tight.

Sample not thermal stable: Use lower oven temperature . Anolyte has too low conductifity .Reduce the value for rel.0 or 0.METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon .Use higher oven temperature .Replace or change the anolyte . check generator electrode. It has no influence to the result.1 mg/g . drift stop . if it is defective. at 170 °C.Add chloroform or another solvent (maximum of 30%) to the anolyte to dissolve the sample Oven: . For samples with very low water content < 30 ppm . If the sample preparation and addition is not done carefully.Extend tmin (minimum titration time) Incomplete sample addition .Use back weighing.Too high value: see above “too high value” . bad repeatability With water standard 1.Clean titration cell and measurement electrode Poor sample preparation and addition Samples of low water content (< 1000 ppm) are always hygroscopic.Replace or repaire generator electrode. contamination with atmospheric moisture occurs.Add sample into KF reagents.use a bigger sample size up to 0.3 g Generator electrode is contaminated The black cover cannot be removed.Replace anolyte .Lengthen vaporization time (increase t max) .Replace anolyte If this doesn’t help. bad repeatability Platinum parts of the generator are colored black Warning: “Conductivity too low” 74 . .2 .0. 10 – 15 minutes .Sample is oxidized: use nitrogen as a purge gas Checking coulometer Out of limits. . Sample not dissolved (emulsion) .Too low value: see above “too low value” if this does not help.Check drift and blank value .Use fix generator current 100 mA . the Coulometer must be adjusted With water Standard KF Oven 1 %.Use start cautious Oven: . Checking drying oven Out of limits.Use smaller sample size Values too high The titration was too fast → overtitration . do not splash to the walls of the cell.

Increase oven temperature .Replace molecular sieves and silica gel in drying tube . drift stop" as a termination parameter. external extraction.2 Volumetric Karl Fischer Titration Problem Possible causes and action to take Titrated solution is dark Drift too high after pretitration of fresh solvent Overtitration .Use higher oven temperature .Increase amount of sample to ensure 10 mg water per sample. . e.METTLER TOLEDO Good Titration PracticeTM in KF Titration 10. Wrong control parameters . Water distribution in the sample not homogeneous .Increase vaporization time.g. .Shake titration vessel The drift remains too high during standby titration Titration stand not protected against moisture .Grease the tapered joints Condition Titration stand . Low water content (<1000 ppm)! .Extend tmax (maximum titration time) .Homogenize sample. titration never ends Wrong termination parameters .Replace silica gel and molecular sieve in the gas drying unit Drift too high after titration of a sample The sample has not completely dissolved and continuously releases water . if possible increase amount of sample.Use t(max) as termination parameter .Reduce sample size Poor repeatability of the results Amount of sample too small .Increase value for relative drift stop.Extend vaporization time (increase t max) . etc. 75 .see above Oven: . drying oven.Check and optimize control parameters.Use longer mixing time or different solvents which dissolves the sample or extracts the water quicker. . e.Increase endpoint potential Oven: water vaporizes very slowly and irregularly .Check whether titration stand is completely tight. Titration stand not protected against moisture . Oven: water is not completely vaporized .Clean platinum pins of the electrode with a paper towel.Use "Rel.The repeatability is strongly dependent on suitable sample preparation and sample addition.g. Side reaction of the sample with the KF reagent . increase t(max) Long titration time.Use different method.

Sample is not thermally stable: Use lower oven temperature .12 g in 40 mL.Use back weighing. Sample not dissolved .Extend vaporization time (increase t max) .Use titrant with 2 or 1 mg/mL Oven: . 15 – 20 minutes .Replace solvent .Sample is oxidized: use nitrogen as a purge gas The results in a series are continuously decreasing Very slow titration with twocomponent titrant Wrong or greatly fluctuating values in the concentration determination with water Dissolving capacity of the solvent is exhausted .Check drift and blank value . Water as standard requires practice The use of water for the concentration determination requires experience to obtain repeatable and accurate results. Determination of the concentration using di-sodium tartrate or Water Standard 10.Reduce the value for rel.55 % at 220 °C.Reduce dVmax and dVmax factor. If the sample preparation and addition is done carefully. drift stop . With water Standard KF Oven 5. For samples with low water content < 400 ppm .4 g Increasing value in the concentration determination with di-sodium tartrate Checking drying oven Out of limits. Di-sodium tartrate has only limited solubility In methanol max. bad repeatability 76 .Replace the solvent frequently.Reduce sample size Single values too high Control parameters too fast (= slight overtitration) .Extend tmin (minimum titration time) Incomplete sample addition .Change solvent or use fresh solvent after every sample.Add chloroform or other solvent to methanol. Poor sample preparation and addition . contamination with atmospheric moisture occurs.METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon . 0. No more sulfur dioxide in the solvent .Use higher oven temperature .Samples of low water content (<1000 ppm) are always hygroscopic. Oven: .0 is a simpler and a more dependable method.Increase sample size up to 0. . The concentration determination is correct only if the di-sodium tartrate has completely dissolved. which dissolves the sample.Change solvent.

C22 V16 C0 V10 C0 Nitrocompounds V3. C0 Peroxides V2. V3.V3.C22 V2. R-I R-NCO Benzophenone Method V2.: benzamide.V4. salicylic acid High pKa value: 2-chlorophenol. o-cresol Side reaction: naphthol. diphenylmethanol Weakly basic pKa >8: Imidazole.V4 C20 Carbamates Carboxylic acid amides Mono-/polycarboxylic acids RO-CONH2 R-CONR´. e. bitumen V4. carbazole Strongly basic: aminopyridine Reaction with methanol: naphthylamine.V4. C0 V2 C20 V15 Low pKa value: phenol.V7 V2. V3. stearamide Weakly acidic: benzoic acid Strongly acidic: malonic acid. indole. anthracene.V5 C20. cresol.V3. V4 C20 V15 C20 V0. V4 V2. V4 C20 Mercaptans V0.1 Organic Chemicals Substance Acetals Aldehydes Mono-/polyalcohols Amines Examples R1-CH-(OR2)2 Chlorobenzaldehyde. C0 Sulfur compounds Phenols V0. R-Br. oxalic acid Oxidizable with iodine: ascorbic acid V2.V5 C20.V3.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11 Karl Fischer Titration: The Method at a Glance 11. C20 V11 C0 V2. nitrobenzaldehyde > C12 Stearyl alcohol. aminophenol Aromatic/aliphatic sulfonic acids sulfides R-S-R´ disulfides R-SS-R´ thiocyanates R-SCN V0.V8 C20 V10.1.1 Solid samples 11.V5 C20 Ethers Linear and cyclic V2. V4 C20 V2. naphthalene > C20 Tar.g. C0 Esters Carboxylic acid ester R-COOR´ Carbonic anhydride ROCOOR´ 77 . toluidine Oxidizable with iodine: aminophenol Method V2.V3 C20 di-Nitrobenzene. nitrotoluene.V4. V4 C20 V2 C20 Substance Halogenated hydrocarbons Isocyanates Ketones Examples R-Cl. anisidine.V4. nitrochlorobenzene Dialkylperoxide R-OO-R Alkylperoxide R-OOH Diacyl peroxide V0. V5 C20 V2.pyren e. V3. C24 Hydrocarbons > C12 Biphenyl. C0 V2.

etc.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. oxides Halogenides Examples Method V30 C30 V34 C32 V31 C32 V21. C34 V10 Na2HAsO3 .1. Insoluble: pigments. 78 . NaSO3 Na2S2O5 SnCl2 Nitrates NaNO3 .g.C40 V2 Adhesives All-purpose glue.: Na3PO4 Silicon oxide. CaO NaCl. Silicon dioxide Silanols R3Si(OH) Na2SO4. C34 V2. bitumen lubricating grease. C32 V31 C32 Thiosulfates Tin(II)salts Na2S2O3. HBO3 . V5 V5 V2 V20 V2 V5 V30. polyurethane. MgCl2 Cu(I) salts: CuCl2 NaH2PO4 . C34 V31 C33 V2. V31 C31. V32 C20. fungicides. ZnSO4 V2. V31 C20. KOH MgO. polypropylene. CaCl2 . glue stick Rubber cement Textile auxiliaries Surfactants powder optical brightener Plastics Polymers Polyethylene. V31 C20. V30 Insecticides. Na2HPO4 tert. H3BO3 NaOH. NaHCO3 Na2CO3 B2O3 . lotion Lipstick Soaps Toothpaste V4. disinfectants Salves. Phosphate. V31 C20. dispersion dyes Waxes.3 Technical products – organic Substance Agrochemicals Dyes Examples Method V2 Substance Petrochemicals Examples Method V12 C0 V7 V5. poly-amides. ski wax Tar. e. C32 Pharmaceuticals Antibiotics. polystyrene. KJ. creams Suppositories Tablets Lyophilized preparations V2 V4. etc. C34 V2. NH4NO3 Nitrites NaNO2 11.1. V32 C21. C32 V15. herbicides Soluble: wool dyes. NaAsO2 KHCO3 . V8 Cosmetics Creams. V5 V12 V2 V40. paraffins: shoepolish. C32 V31 C32 Sulfates Silicon compounds Substance Phosphates Examples Method V2. PVC. V32 C20. V31 C32 V2.2 Inorganic chemicals Substance Arsenic compounds Bicarbonates carbonates Boron compounds Hydroxides. V32 C21. indicator dyes. multipurpose grease V2 V2.

.4 Technical products . Zwieback. (V5) V6 C23 V32 C34 V8 V2 V6 V5 79 . sea salt V23 V24. cement Adherent moisture Zeolites Laundry detergent with brightener (hydroxides. V23 Cacao. sea salt Total water: plain salt.1.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. candy. jam Honey. mixed spice Mustard Adherent moisture: plain salt. mayonnaise Shortening. dried vegetables and fruits Hazelnuts. (V30) Cheese. V21 Mortar. tea. V5 V5 Sugar and sugar products V13 V13 Sugar: total water cont. wood Cellulose powder Wool. pudding powder. margerine. corn. almond paste Instant ice tea. instant coffee. rye. curry.1. perborates) without brightener Total water V30 V2 11.1. jellied fruits. noodles. tobacco. ice cream Dried albumen Powdered milk V2 V13 V2. meat spread. noodles. V23 V30. jelly Sugar: adherent moisture Chocolate Spices Pepper. C30 V2 V20 Paper. potato chips Potato flakes Dough.almonds instant coffee Fats Butter. broth Biscuits. caramel. hardened fat V4. gummi bears. wheat. V23 Vegetable products V22. silk 11. Zwieback Yogurt. (V25) V22.inorganic Substance Building materials Fertilizers Examples Method V32 (C34) V6 Substance Minerals Detergents Examples Method V32 V30. coffee beans. plaster.6 Food Substance Protein products Examples Method V23 Substance Grains and starchy foods Examples Method V13.5 Technical natural products Substance Cellulose products Fibrous materials Examples Method V30.

xylene C7 to C14 gasoline. hexanol. pentane. acrylic acid V15 C0 V1 C1 V1 C1 V1 C1 V1 C1 Acid amides Dimethylformamide Sulfides. cyclohexene. dodecane > C14 heavy oil. methylal C1 to C7 hexane. methylethylketone Ketones V10 C10 80 . acetic acid > C2 propionic acid. crude oil. isobutane. nitrotoluene. dioxane. toluene. anisole Methyl benzoate.2. diamine Easily oxidized with iodine: hydrazine. cyclohexane. petroleum. chinoline Strongly basic: alihatic amines N-butylamine. benzaldehyde V11 C0 saturated and unsaturated V4 C1 Alcohols Propanol. C0 Ethers Esters Halogenated hydrocarbons Dimethylether. HCl Nitrobenzene.1 Organic and inorganic chemicals Substance Acetals Examples Method V1 C1 Substance Hydrocarbons Examples Method V1 C1 Acetal. benzene. paraffin Aldehyde Acetaldehyde. hydroxylamine V1 C1 V1 C1 Mineral acids V5 C30 V15 C0 Amines H2SO4. hexylamine Reaction with methanol: aniline. chlorobenzene. HNO3. nitrochlorobenzene Acetonitrile V16 C0 Nitrocompounds V1 C1 V10 C0 Nitriles V1 C1 V0 C0 Peroxides H2O2 V15 Carboxylic acids C1 to C2 formic acid. t-butyl chloride.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. C1 Sulfurcompounds V1 C1 V0. ethylal.2 Liquid samples 11. ethyl acetate Methyl chloride. toluidine. acetophenone. chlorotoluene Acetone. disulfides sulfonic acids Mercaptans V1. benzyl alcohol Weakly basic: N-methyl aniline heterocyclic amines pyridine.

transformer oil. 81 . refer to chapter 11. cream. silicon oil Motor oils V5 C1 V30 C30 For more details on the sample preparation. wine. brake fluid. shampoo Method V1 V1 V1 V1 V4 Tensides and detergents Aqueous emulsions Milk products: milk.3.2. massage oil Vegetable oils Technical oils Hydraulic oil. tinctures Cosmetics: perfume. sunflower oil Pharmaceuticals and cosmetics: ethereal oils. sample input and titration methods. fungicides Acrylic enamels Emulsions in solvents V1 V1 V29 V4 C1 V7 V4 C1 V4 C1 Agrochemicals (sprays): insecticides Synthetic enamels Foods: salad oil. liquor Pharmaceuticals: extrakts. condensed milk Tensides and detergents Agrochemicals (sprays): herbicides.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.2 Foods and technical products Substance Aqueous solutions Examples Foods: spiced sauce: soy sauce beverages: beer.

3 Titration Methods 11.120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: KF solvent / chloroform 1:1 to 1:2 Stir time: 60 .3.120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / chloroform 1:5 Stir time: 60 .10 minutes V4 V5 V6 V7 V8 V10 V11 V12 82 .10 minutes Direct titration methanol free Titrant: two comp. dProcedure V1 Direct titration Titrant: Solvent: Stir time: Direct titration Titrant: Solvent: Stir time: two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 10 s two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 60 .120 s Delay time: 7 seconds. reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Stir time: 30 – 60 s Direct titration methanol free Titrant: two comp. These can be also performed using the one-component reagent. reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Start immediately (autostart) Direct titration with heat (at 50°C) Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent Stir time: 5 .1 Volumetric methods The methods have been developed using 2-component reagents.120 s Direct titration with added formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 5 .120 s Direct titration with added 1-decanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / 1-decanol 1:1 Stir time: 60 . In this case methanol is used as a solvent.120 s V2 V3 Direct titration with added 2-propanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / propanol 1:1 Stir time: 60 . Direct titration with added toluene Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / toluene 1:1 Stir time: 60 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.

150°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 . Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with methanol at 50 °C Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide 1:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide/methanol 8:2:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 With drying oven at 110 .120 s Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 5 g benzoic acid Stir time: 1-2 minutes External extraction with methanol at room temperature Titrant: two component reagent 5 mgH2O/mL Solvent: 30 mL KF solvent External extraction with methanol at room temperature in sonicator Remove aliquots of extraction solution over membrane filter with syringe.15 minutes Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 20 mL buffer or 7g imidazole Stir time: 60 . 50°C Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 10 .20 min Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated solvent and inject entire solution into titration cell and titrate.220°C Titrant: two component reagent 5 or 2mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .METTLER TOLEDO Good Titration PracticeTM in KF Titration V13 Direct titration with added formamide and heat. Titrant: two component reagent 2 mg H2O/mL Solvent: 50 mL KF solvent Side reaction: KF titration not possible V15 V16 V20 V21 V22 V23 V24 V25 V29 V30 V31 V32 V40 V0 83 .20 min With drying oven at 160 .20 min With drying oven at 300°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .

3.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.2 Coulometric methods Method C1 Procedure Direct titration Anolyte: Catholyte: 100 mL anode reagent 5 mL cathode reagent C5 Direct titration with added chloroform Anolyte: 70 mL anode reagent and 30 mL chloroform Catholyte: 5 mL cathode reagent Direct titration methanol free Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones External extraction with methanol or external dissolution in methanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with Methanol in sonicator Remove aliquots of extraction solution over membrane filter with syringe. Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with 1-decanol or external dissolution in 1-decanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with chloroform or external dissolution in chloroform Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction or external dissolution in chloroform (methanol free) Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones With drying oven at 110-130°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 140-150°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 160-190°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 200-250°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 300°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated anolyte and inject entire solution into titration cell and titrate. Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Coulometric determination not possible C10 C20 C21 C22 C23 C24 C30 C31 C32 C33 C34 C40 C0 84 .

gummi bears. for very thick pastes drill hole in bottom of syringe. almond paste. the moisture will be pressed out with pre-heated syringe (with needle Ø 0. No further preparation necessary. 60° C. S10 S2. tea. At room temp. Inject into titration cell. S5 S10 S8 Paraffins. chocolate Method S1 S1. cooled analysis mill. S8 S10 Property Soft.: CaCO3 . brittle Soft. pepper. brittle Hard natural products Fibrous natural products Tenacious products Soft products Hard. or up to approx. Homogenize sample well. S2 S1.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.) Homogenize sample well. Zwieback Dried vegetables and fruits. meat Jellied fruits. noodles. 1-decanol. After sample removal keep sample sealed. formamide). yogurt Salts. creams gel. tobacco. (Pre-heat syringe with hair dryer or in drying oven. resinous Waxes Examples Butter. Cut in small pieces with scissors or knife. jelly. After sample removal keep sample sealed. active ingredients Na-tartrate S9 S12 11. SiO2 Salts. S11 S4.g. Use syringe with needle Ø 1. Stir. S3 S10. 1-decanol. shake or sonicate. rocks e. paper.) S8 S9 S10 syringe with needle Ø 0. wool. honey. meat grinder. broth Hardened fat. Break and disperse with high-speed mixer (up to 24000 cpm) in external extraction solvent (methanol. (Select stir time so that sample dissolves completely. pastes Pulverized soluble Salves. Pulverize with mixer. S10 S11 S4. greasy Examples Minerals.8 mm ) Fill in backend of syringe Procedure Grind in sealed. Let solids settle and remove aliquot of remaining solution with syringe.4. shoepolish Creams. potato flakes Tar. In external extraction solvent (methanol.4 Sample preparation and input 11. Pulverize with mortar. S10 S11 S10.1 Solids: Characteristics Property Very hard Hard. margarine Phenols. ice cream. cristalline products Wheat. Dissolve sample or extract water. coffee. Melt sample.8 mm S11 S12 syringe without needle (Fill very thick samples in back of syringe) weighing boat 85 .g. napthalene.5 mm or without needle.4. bitumen Method S7. Press through small holes e. silk Cheese. greasy Soft. S3 S2. formamide). S11 S6. almonds.2 Solids: Sample input Method S1 S2 S3 S4 S5 S6 S7 Sample input finely ground sample with weighing boat finely ground sample with weighing boat finely ground sample with weighing boat with spatula with spatula or weighing boat with spatula or weighing boat with spatula Do not use syringe. Use grate to reduce size.

8 mm) Injection with syringe Procedure Fluid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe. crude oil. .Remove sample immediately. gasoline. . .15 °C . Samples with high moisture content (> 50%) Rinse syringe with sample 2-3 times.Cool sample to approx.8 mm).Rinse syringe with sample 2-3 times (pull up and discard) and condition for 5 minutes. acetone. glycerine Hexane.3 Liquids: Characteristics Property Liquid Turbid Low boiling point Hygroscopic Low moisture content Non-hygroscopic.Homogenize thoroughly by shaking or stirring prior to sample removal. petroleum. Turbid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.4.Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.8 mm ME-71482 ME-71484 Septum NS24 ME-23950 Three-hole adapter ME-23982 86 . average moisture content High moisture content Inhomogeneous (> 50%) (< 1000 ppm) 5 . aqueous emulsions Acrylic enamels.5 Accessories for sample input Syringe Injection needle Weighing boat.8 mm) Inhomogeneous emulsions . For each titration use 1 mL syringe (with needle Ø 0.4 Liquids: Sample input Method L1 Sample input Injection with syringe (with needle Ø 0.Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe. salad oil Perfume. .The pressure loss during sample removal must be compensated with dried air. Boiling point 5 .Keep sample in a septum flask.2 mm ME-71483 ME-23951 ME-51107668 10 mL 0. 0°C in ice bath. L2 L3 L4 L5 Injection with syringe L6 Injection with syringe after sample homogenization (with needle Ø 0. Hygroscopic sample or low moisture content (< 1000 ppm) .4. 11. . glass Visco-Spoon™ 1 mL ME-71492 1.5 mm) Injection with syringe after cooling sample (with needle Ø 0.15°C Examples Propanol.Inject sample into titration cell through septum or needle hole of three-hole adapter with 10 mL syringe (with needle Ø 0. toluene. detergents. acetic acid Silicon oil.4. . H2SO4. glycerine Acetaldehyde Methanol. cream Method L1 L2 L3 L4 L4 L1 L5 L6 11. acetone.8 mm) Injection with syringe (without or with needle Ø 1. after-shave Beverages.8 mm) to remove fresh sample from sample flask and inject this into titration cell through septum or needle hole of three-hole adapter. synthetic enamels. milk.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.

BUNSEN.. Part V.. Potentiometric measurements”.. 75. WERNIMONT. W. “Mechanism and reaction rate of the Karl Fischer titration reaction. G. J.. „Karl-Fischer Reagentien ohne Pyridin.. [10] GRÜNKE.. 394 . 305-315 (1976). Chem. J. Chem. Anal. [8] SCHOLZ. J. 1999 (in German). . Electroanal. J. “Karl-Fischer Reagentien ohne Pyridin“. E. SCHOLZ. Anal. WÜNSCH. Einkomponenten Reagentien“. VERHOFF. Ind. A. 265 (1853).. SMITH. 31 (2). 306. Electroanal. 407-415 (1978). „Wasserbestimmung mit Karl-Fischer-Lösung“. Fresenius Z.. 71.. SCHOLZ. R. Part II. Fresenius Z. Chem. Chem. J. 2407 . Thesis University of Hannover. Analytical implications”. Electroanal. GRÜNKE. Fres. KOK. SCHOLZ. MEYER.. Chem. Liebigs Ann. Diploma-Thesis at the University of Hannover / Germany.. „Karl-Fischer Reagentien ohne Pyridin. HOPFKINSON. Anal. Both publications from: SEUBERT. Z. G. 94.J.6 References [1] [2] FISCHER. E. 312. Chim.. Chem. SEUBERT A. E. “Stöchiometrie und Kinetik der Karl-Fischer –Reaktion in Methanol als Reaktionsmedium”. K. „Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern“. 309.. “Reaktionsmechanismen in der Karl-Fischer-Lösung“. COFINO. C. Chem. First and second order catalytic currents at a rotating disk electrode“.2412 (1939). W. Chem. E... J. 334. 1. E. “Nebenreaktionen in Karl-Fischer-Reagenzien ”.. Chem.W.C. W. Anal. Chem.C. SEUBERT A.. MITCHELL jr. 309.. G. Fres. 203 . „The Dead-Stop End Point – As Applied to the Karl Fischer Method for Determining Moisture“.C. „Karl-Fischer Reagentien ohne Pyridin. [9] WÜNSCH. E. 61.4. Rotating ring disk electrode meassurement . VERHOFF. Anal. E. S. 460-464 (1982).. 705-717 (1976).METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. Fresenius Z. Electroanal. E. VERHOFF. Chem. Part I.396 (1935). Neue Eichsubstanzen“. 86. 215 – 219 (1959). SCHOLZ. Fresenius Z. „Kinetics and stoichiometry in the Karl Fischer solution“. “Mechanism and reaction rate of the Karl Fischer titration reaction.M. “Determination of Water by Titration with Coulometrically Generated Karl Fischer Reagents”.. Anal. „Karl-Fischer Reagentien ohne Pyridin Genauigkeit der Wasserbestimmung“. “Untersuchungen zur Karl-Fischer-Reaktion”.C.. Auflage. 15 (4). Part IV. 93.. Anal. WÜNSCH.. Zweikomponenten Reagentien mit Imidazol“. Chem 368. Rotating ring disk electrode meassurement“. E. 123-125 (1981). Acta. 303. 30-32 (1981). Soc. J. 16-21 (1989) (in German). Fresenius Z. Chem.. Amer. „Mechanism and reaction rate of the Karl Fischer titration reaction. BARENDRECHT.C. Chem.207 (1980). Anal. Chem. BRYANT. 75-80 (1978). Eng. A. J.. D. Fresenius J. Part III. Anal.S. J. 334. “Analytical Procedures Employing Karl Fischer Reagent I. Angew. 86.. “Mechanism and reaction rate of the Karl Fischer titration reaction. G. P. M. BARENDRECHT. 395-403 (1977). S. Ed. Chem. 394 . Nature of the Reagent”. M. 1988 (in German). J.. PhD. 256-260 (1989) (in German). 272 – 274 (1943). Verlag Chemie Weinheim (1954) / (in German). See literature references in: EBERIUS. Anal. Z. BARENDRECHT. VERHOFF. Chem. [3] [4] [5] [6] [7] 87 . J. VERHOFF.comparison with the aqueous system“.396 (1981). Th. BOYD. 48. Anal. “Mechanism and reaction rate of the Karl Fischer titration reaction. F. 139-147 (2000).

1985. DE AGOSTINI A.. 11..METTLER TOLEDO Good Titration PracticeTM in KF Titration [11] LANZ. Food Chemistry 96. „Eugen Scholz Reagents for Karl FischerTitration“. 431-435 (2006)..30918 Seelze / Germany. 1989 (German) 88 . G. "Coulometric Karl Fischer titration with a diaphragm-free cell: Cell design and applications". D. DE CARO C.. Diploma-Thesis at the University of Hannover / Germany. 2006. E.. Sigma-Aldrich Laborchemikalien GmbH.5 Additional literature HYDRANAL®-Manual. K. SCHÖFFSKI.. 1984. „Wasserbestimmung durch Karl-Fischer-Titration .Theorie und Praxis“.. Darmstadt / Germany. „Untersuchungen einer Karl-Fischer-Reaktion“.A. GIT Verlag GmbH. „Karl Fischer Titration“. M. RÜEGG K. SCHOLZ. Springer Verlag Berlin. WIELAND.

WP: This is what we get from the calculation in the KF method. The sample P used for the extraction is not dissolved.1 Formula for the external extraction Principle: • • The water amount (in grams) after extraction is equal to the water amount before extraction. 89 . Water amount after extraction = Water amount before extraction WTOT•(mL + (mP•WP) ) = WP•mP + WL•mL where Water content in the sample P (% or ppm).METTLER TOLEDO Good Titration PracticeTM in KF Titration 12 Appendix 12. For ppm : R (ppm ) = 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 10 6 − C ⎝ mext since 1 = 106 ppm. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent C ⋅ msol + C ⋅ mext ⋅ R = R ⋅ mext + B ⋅ msol C ⋅ mext ⋅ R − R ⋅ mext = B ⋅ msol − C ⋅ msol R ⋅ (C ⋅ mext − mext ) = B ⋅ msol − C ⋅ msol R= 1 ⋅ (B ⋅ msol − C ⋅ msol ) (mext ⋅ (C − 1)) R= R= 1 ⋅ (C ⋅ msol − B ⋅ msol ) (mext ⋅ (1 − C )) since 1 1 =− 1− C C −1 1 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 1 − C ⎝ mext R (%) = 100 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 100 − C ⎝ mext since 1 = 100%. % or ppm). WTOT : Water content of the supernatant extraction solvent (% or ppm) WL : mL : mP : Thus: 1) 2) 3) 4) 5) 6) 7) For % : C ⋅ [msol + (mext ⋅ R )] = R ⋅ mext + B ⋅ msol R C B msol mext Blank value (water content of the solvent.

2 Formula for the external dissolution Principle: The water amount (in grams) determined by titration is the sum of the water amounts present in the solvent and in the sample.55% (potassium citrate monohydrate) The water content is declared on a test certificate supplied with every vial.1% SIGMA-ALDRICH HYDRANAL®-Water Standard 0. Blank value (water content in% or ppm) of the solvent. ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ 12. in % or ppm.3 Standards for Karl Fischer coulometry a) For direct measurements: VWR/VWR/MERCK APURA water standard 0.00 mg/g (1000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5. Thus.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. The sample P used for the external dissolution is completely dissolved into the solvent.1 mg/g (100 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 1. Total water content (sample + solvent). Water amount after dissolution = Water amount before before dissolution WTOT•(mL + mP) = WP•mP + WL•mL where WP: WTOT : WL : mL : mP : Thus: 1) 2) 3) 4) C ⋅ [msol + mext ] = R ⋅ mext + B ⋅ msol Water content in the sample P (% or ppm) This is what we get from the calculation in the KF method. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent R C B msol mext C ⋅ msol + C ⋅ mext = R ⋅ mext + B ⋅ msol R ⋅ mext = C ⋅ msol + C ⋅ mext − B ⋅ msol ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R = C ⋅⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % and ppm: ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%. the total volume is increased. 90 .01% VWR/VWR/MERCK APURA water standard 0.

more solvent can be added to the anolyte. chlorinated hydrocarbons (up to C10). esters.2 For samples that are poorely soluble in methanol or ethanol These include: etherial oils. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Ethanol-based reagents: anolyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) Methanol-based reagents: electrolyte:HYDRANAL® Coulomat AD (SIGMA-ALDRICH) - For cells without diaphragm: - APURA combiCoulomat fritless (VWR/VWR/MERCK) 12.e.4. 30% hexanol APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% hexanol catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit For cells without diaphragm: 91 . ointments. etc. ethers. part of the water content is not measured. A number of different anolytes are available to dissolve the various types of samples encountered in practice. 12. etc. Octanol or hexanol can be added to the anolyte to improve the solubility of these samples. hydrocarbons (C10 to C20). the water content determined is lower than the actual water content of the sample. nitrocompounds. alcohols. In this case. Alternatively.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. acetamide. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG-H (SIGMA-ALDRICH) contains approx. an emulsion is formed. the sample must completely dissolve in the anolyte. the anolyte must be immediately replaced. edible oils.4. If the sample does not completely dissolve.4 Reagents and solvents for coulometric analysis To determine its total water content. This is limited to a maximum of 30% to prevent the conductivity from falling too low.1 For samples that are soluble in methanol or ethanol These include: hydrocarbons (up to C10). i. This means that if an emulsion is formed in the anolyte.

Chloroform must be added to the anolyte to ensure the solubility of these samples.4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal or an acetal and water.4. For cells without diaphragm: - Notes on ketones: - - 92 . transformer oils. If you measure ketones regularly. For cells with diaphragm: Methanol-free reagents: anolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat CG-K (SIGMA-ALDRICH) Methanol-free reagents: electrolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) When changing from normal KF anolytes to ketone reagents. the entire titration cell must be thoroughly cleaned because even traces of methanol may cause serious interferences. silicone oils. This is limited to a maximum of 30% in order to prevent the conductivity from becoming too low. hydrocarbons (above C20). For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat A (SIGMA-ALDRICH) + 20% chloroform HYDRANAL® Coulomat AG (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% chloroform catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat fritless (VWR/VWR/MERCK) + 30% chloroform For cells without diaphragm: - 12. Acetal formation: Ketal formation: CH3COH + 2 CH3OH → (CH3)2CO + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O Special methanol-free reagents must be used for these substances. we recommend the use of a second titration cell. etc.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 20% hexanol APURA CombiCoulomat fritless (VWR/VWR/MERCK) + 20% hexanol 12.3 For samples that are insoluble in methanol or ethanol These include: petroleum oils.4.

It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes.g.g. To do this. the substances can. e.2 mL to 0. formic acid. It is important to note that alcohols that react with ketones should not be titrated in this reagent.g. With Karl Fischer titrations of acidic and basic samples.METTLER TOLEDO Good Titration PracticeTM in KF Titration - If you have titrated a number of ketone samples. Choose relatively small samples (approx. The larger the sample. This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value). etc. the more important the effect of side reactions becomes. amines: - 93 . acetic acid. Short chain aldehydes (e. Coulometric KF titration cannot be used to determine these compounds. the drift is higher because of the very slow side reaction. it is possible that the anolyte is exhausted after a few days even though no further titrations have been performed. Fill the anode compartment with approx. Measure the pH with a glass electrode adjusted with aqueous buffers. The special reagent for ketones can also be used for other samples. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult.4.5 to 7 (see Section 1. The use of imidazole increases the pH value in the anolyte. however. Fill the anode compartment with approx.2). - - Notes on aldehydes: - - 12.g. with reactive ketones such as cyclohexanone use only 0. take an aliquot of anolyte from the titration cell. i. 80 mL of anolyte and 20 mL HYDRANAL® buffer.5 mL. Use the HYDRANAL® buffer (SIGMA-ALDRICH). Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte.: - For basic samples. the pH value of the anolyte must be adjusted to the range 5. e.e. 1 mL). acetaldehyde) are oxidized at the anode with the formation of water. easily be measured with volumetric KF determination.5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift. - For acidic samples. In these cases the pH value of the anolyte should be measured. Aromatic aldehydes (e. The measurement should not be performed in the titration cell because the electrode introduces too much water. After a longer standby period. Basic samples must be neutralized with salicylic acid or benzoic acid. benzaldehyde) can also be determined by coulometric KF titration. 90 mL of anolyte and 5 g salicylic acid or benzoic acid.

the result determined is lower than the actual water content. hydrocarbons (C10 to C20). i.55% (potassium citrate monohydrate).METTLER TOLEDO Good Titration PracticeTM in KF Titration 12.0 mg/g (10’000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5.6. A number of different anolytes are available to dissolve the various types of samples encountered in practice. 12. alcohols. If it does not completely dissolve.1% VWR/VWR/MERCK APURA® water standard 1% SIGMA-ALDRICH HYDRANAL®-Water Standard 1. the anolyte must be immediately replaced. In this case. This is limited to a maximum of 50%. chlorinated hydrocarbons (to C10). ethers. etc. esters.0 mg/g (1000 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 10. nitrocompounds. The water content is declared on a test certificate supplied with every vial. ointments.e. more solvent can be added to the anolyte 12.1 For samples soluble in methanol or ethanol These include: hydrocarbons (to C10). Octanol or hexanol can be added to the anolyte to improve the solubility of these samples. edible oils.6 Titrants and solvents for volumetric analysis The sample must be completely dissolved in the anolyte to determine the total water content.2 For samples poorly soluble in methanol or ethanol These include: etherial oils. One-component reagents: 94 . One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: Dry methanol Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent Ethanol-based: Titrant: HYDRANAL® Titrant E Solvent: HYDRANAL® Solvent E (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: (SIGMA-ALDRICH) (VWR/Merck) - (SIGMA-ALDRICH) (SIGMA-ALDRICH) 12. an emulsion is formed.6.5 Water Standards for Karl Fischer volumetric titration a) For direct measurements: VWR/VWR/VWR/MERCK APURA® water standard 0. etc. acetamide. Alternatively. In this case. part of the water content is not measured.

hydrocarbons (above C20).4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal. MH apura® CombiSolvent Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM. etc. or an acetal. Acetal formation: Ketal formation: CH3COH + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O (CH3)2CO + 2 CH3OH → Special methanol-free reagents must be used for these substances. transformer oils.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® LipoSolver CM. with the formation of water. One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® Solver (Crude) apura® CombiSolvent Fats Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM.6. One-component reagents: 95 . Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12.6. silicone oils.3 For samples insoluble in methanol or ethanol These include: petroleum oils. Chloroform must be added to the anolyte to ensure the solubility of these samples. Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (VWR/Merck) Two-component reagents: - (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12. This is limited to a maximum of 50% in order to prevent the conductivity from becoming too low.

In these cases the pH value of the anolyte should be measured. amines: 96 . With Karl Fischer titrations of acidic and basic samples. It is important to note that alcohols that react with ketones should not be titrated in this reagent. It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-free: Titrant: Solvent: HYDRANAL® Composite 5 K apura® CombiTitrant 5 Keto (SIGMA-ALDRICH) (VWR/Merck) HYDRANAL® Medium K (SIGMA-ALDRICH) HYDRANAL® Working Medium K HYDRANAL® KetoSolver apura® CombiSolvent Keto (VWR/Merck) Notes on ketones: When changing to ketone reagents. e.5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift.g. Aromatic aldehydes (e. we recommend the use of a second titration cell.5 mL.2 mL to 0. The measurement should not be performed in the titration cell because the electrode introduces too much water. however. benzaldehyde) can also be determined by coulometric KF titration. i. 80 mL of anolyte and 20 mL HYDRANAL® buffer. the substances can. the pH value of the anolyte must be adjusted to the range 5. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult. the drift is higher because of the very slow side reaction. take an aliquot of anolyte from the titration cell. e. etc. To do this. Coulometric KF titration cannot be used to determine these compounds. The use of imidazole leads to a high pH value in the anolyte. with reactive ketones such as cyclohexanone use only 0. The larger the sample.g. Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte. the entire titration cell must be thoroughly cleaned because even traces of methanol can cause serious interference.2). If you measure ketones regularly.: - For basic samples. the more important the effect of side reactions becomes. easily be measured with volumetric KF determination. Short chain aldehydes (e. - Notes on aldehydes: - - 12.g. formic acid. Measure the pH with a glass electrode adjusted with aqueous buffers. Choose relatively small samples (approx.e.5 to 7 (see Section 1. This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value). acetic acid. Use the HYDRANAL® buffer (SIGMA-ALDRICH).g. acetaldehyde) are oxidized at the anode with the formation of water. The special reagent for ketones can also be used for other samples. - For acidic samples. 1 mL). Fill the anode compartment with approx.6. If you have titrated a number of ketone samples.

1 One-component reagent Composition: sulfur dioxide. Ignition temp.4 Safety data for the KF-components and auxiliary solvents: sulfur dioxide: iodine: diethyleneglycolmonomethylether: 2-methoxyethanol: MAK-value: 200 ppm MAK-value: 0.: 11 °C MAK value: 200 ppm Highly flammable. The KF solvent contains: sulfur dioxide. tetrachloromethane. 90 mL of anolyte and 5 g salicylic acid or benzoic acid. Keep container tightly closed and far removed from open flames or sparks. Disposal: as an organic solvent. oxidant Ignition temp. swallowed or allowed to contact skin. Safety: flammable to extremely flammable. 2-methoxyethanol). Health hazard when inhaled.: 28 °C MAK value: 100 ppm Flammable. Keep container tightly closed. and solvent (methanol. Keep away from open flames or sparks. 2methoxyethanol or diethyleneglycolmonomethylether). Keep container tightly closed. Do not let reagent contact skin or eyes. poisonous when inhaled or swallowed. Poisonous when inhaled or swallowed. Irritant when inhaled. xylene or trichloroethaylene). 13. iodine. Disposal: as an organic solvent. 13. 13. Ignition temp.: 46 °C MAK value: 5 ppm Flammable. Health hazard when inhaled. Safety: flammable to extremely flammable. Health hazard when inhaled. chloroform. 2-methoxyethanol. swallowed or allowed to contact skin. Disposal: as an organic solvent. Potential teratogen. 2methoxyethanol or diethyleneglycolmonomethylether). Ignition temp.1 ppm. Fill the anode compartment with approx. Keep away from open flames or sparks. Do not let reagent contact skin or eyes. sulfur dioxide. Do not let reagent contact skin or eyes. buffer (imidazole) and solvent (methanol. Irritant when inhaled. Health hazard upon inhalation. Irritant when inhaled. buffer (imidazole). swallowed or allowed to contact skin.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Basic samples must be neutralized with salicylic acid or benzoic acid. buffer (imidazole) and solvent (methanol.3 Reagents for coulometry: Composition: iodine. 13 Hazards and waste disposal tips 13. Skin irritant.: 87 °C Ignition temp. Safety: Highly flammable.2 Two-component reagent: Composition: iodine and solvent (methanol.: does not burn MAK vlaue: 200 ppm 97 methanol: o-xylene: chloroform: .

: 6°C MAK value: 20 ppm Extremely flammable. Ignition temp.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1-decanol: formamide: toluene: Health hazard when inhaled.: inflammable MAK value: 20 ppm Irritant for skin and eyes. Ignition temp. Ignition temp. Irreversible damage possible. Potential teratogen.: 95 °C Irritant for skin and eyes. Health hazard upon inhalation 98 .

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evaluation. www. This brochure specifically focuses on Good Titration Practice in water determination using coulometric and volumetric Karl Fischer Titration. specification of the analytical requirements and purchase decision 2. ME-51725145A Markt Support AnaChem .e. Evaluation of the appropriate titration system (DQ) i. Switzerland Tel.Good Titration Practice in water determination Good Titration Practice™ (GTP) in general encompasses three important steps: 1. +41-44 806 77 11 Fax +41-44 806 73 50 Subject to technical changes.com For more information Mettler-Toledo AG. development of SOPs and maintenance of the validated state of the analytical system. Analytical Sonnenbergstrasse 74 CH-8606 Schwerzenbach. method validation. ©09/2009 Mettler-Toledo AG Printed in Switzerland. The GTP KF brochure and the application brochure 38 containing dedicated applications on samples from various industry segments.mt. are two powerful tools which are meant to facilitate your daily water determination analyses and to contribute to reliable results over the whole lifetime of your instrument. Routine operation including PQ. It outlines specific aspects in developing and maintaining a good routine operation with METTLER TOLEDO Compact Coulometric and Volumetric KF as well as Excellence titrators. Installation of the selected analytical system comprising IQ and OQ and training of personnel 3.